CN112301347B - Copper or copper alloy micro-etching agent, preparation method and micro-etching method - Google Patents
Copper or copper alloy micro-etching agent, preparation method and micro-etching method Download PDFInfo
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- CN112301347B CN112301347B CN201910676657.2A CN201910676657A CN112301347B CN 112301347 B CN112301347 B CN 112301347B CN 201910676657 A CN201910676657 A CN 201910676657A CN 112301347 B CN112301347 B CN 112301347B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
Abstract
The invention discloses a copper or copper alloy microetching agent which comprises sulfuric acid, hydrogen peroxide, citric acid and/or citrate, acetic acid and/or acetate, sulfamic acid and/or sulfamate, glycerol and/or butanol, trihydroxypropyl hydroxyethyl ethylenediamine, N-methylmorpholine, 2-ethylhexyl sulfate sodium salt and water. According to the invention, through the mutual matching of the components, the copper or copper alloy micro-etching agent with good stability, long service life and good micro-etching effect can be obtained, and the surface brightness and the oxidation resistance of the copper or copper alloy treated by the micro-etching agent are good.
Description
Technical Field
The invention relates to the field of metal surface chemical treatment, in particular to a copper or copper alloy micro-etching agent, a preparation method and a micro-etching method.
Background
Microetching, a good wet chemical process, can effectively remove impurities, oxides and other residues from the surface of a material, and can also form fine irregularities on the surface of the material, thereby roughening the surface. Copper microetching agents are widely used in the copper surface treatment of microelectronic products and components.
The traditional copper microetching agent mainly consists of peroxide or persulfate, but the polishing effect of the copper microetching agent is not ideal; if the copper surface is exposed in the air for more than ten seconds after the micro-etching treatment, the copper surface is discolored; the corrosion phenomenon of the primary battery occurs in the element after the micro-etching treatment; the working solution is unstable and easy to decompose, which causes much inconvenience in actual operation; furthermore, with the development of technology, the precision requirements of circuit boards and components are higher and higher, and the requirements on the micro-etching rate are also higher.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a microetching agent for copper or copper alloys which has high stability, a long life and a high microetching effect, and which has a high surface brightness and a high oxidation resistance when the copper or copper alloy is treated with the microetching agent.
In a first aspect of the present invention, there is provided a copper or copper alloy microetching agent, comprising: 27-50g/L of sulfuric acid, 15-30g/L of hydrogen peroxide, 1-14 g/L of citric acid and/or citrate, 1-6 g/L of acetic acid and/or acetate, 0.4-2g/L of sulfamic acid and/or sulfamate, 3-10g/L of glycerol and/or butanol, 1-12g/L, N g/L of trihydroxypropyl hydroxyethyl ethylenediamine, 0.02-0.6g/L of 2-ethylhexyl sulfate sodium salt and 0.01-0.8g/L of water.
According to one embodiment of the present invention, the microetching agent includes: 30-45g/L sulfuric acid, 18-28g/L hydrogen peroxide, 3-11g/L citric acid and/or citrate, 2-4g/L acetic acid and/or acetate, 0.7-1.6g/L sulfamic acid and/or sulfamate, 5-9g/L glycerol and/or butanol, 2-10g/L, N g/L trihydroxypropyl hydroxyethyl ethylenediamine, 0.04-0.5 g/L2-ethylhexyl sulfate sodium salt, and water.
According to one embodiment of the invention, the weight ratio of acetic acid and/or acetate salt to sulfamic acid and/or sulfamate salt in the microetching agent is (3-1): 1.
according to one embodiment of the invention, the weight ratio of sulfuric acid to citric acid and/or citrate in the microetching agent is (10-3): 1.
in a second aspect of the invention, a method for preparing a copper or copper alloy microetching agent is provided, wherein sulfuric acid, hydrogen peroxide, citric acid and/or citrate, acetic acid and/or acetate, sulfamic acid and/or sulfamate, glycerol and/or butanol, trihydroxypropyl hydroxyethyl ethylenediamine, N-methylmorpholine and sodium 2-ethylhexyl sulfate in the copper or copper alloy microetching agent are dissolved in water to form the copper or copper alloy microetching agent.
According to one embodiment of the invention, the preparation method of the copper or copper alloy microetching agent comprises the following steps:
a. adding sulfuric acid into a proper amount of water, stirring and dissolving;
b. adding citric acid and/or citrate, sulfamic acid and/or sulfamate and 2-ethylhexyl sulfate sodium salt into the solution obtained in the step a, and stirring for dissolving;
c. b, adding hydrogen peroxide into the solution obtained in the step b, and stirring for dissolving;
d. and c, adding glycerol and/or butanol, trihydroxypropyl hydroxyethyl ethylenediamine and N-methylmorpholine into the solution obtained in the step c, and stirring and dissolving to obtain the microetching agent.
In a third aspect of the present invention, there is provided a microetching method using the microetching agent, wherein the microetching agent is brought into contact with the surface of the copper or copper alloy substrate to perform an etching treatment.
According to one embodiment of the invention, the microetching temperature is 25-35 ℃ and the microetching time is 60-300 s.
The copper or copper alloy micro-etching agent with good stability, long service life and good micro-etching effect can be prepared by adopting the mutual matching of sulfuric acid, hydrogen peroxide, citric acid and/or citrate, acetic acid and/or acetate, sulfamic acid and/or sulfamate, glycerol and/or butanol, trihydroxypropyl hydroxyethyl ethylenediamine, N-methylmorpholine and 2-ethylhexyl sulfate sodium salt, and the surface of copper or copper alloy treated by the micro-etching agent has good brightness and good oxidation resistance.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In a first aspect of the present invention, there is provided a copper or copper alloy microetching agent, comprising: 27-50g/L of sulfuric acid, 15-30g/L of hydrogen peroxide, 1-14 g/L of citric acid and/or citrate, 1-6 g/L of acetic acid and/or acetate, 0.4-2g/L of sulfamic acid and/or sulfamate, 3-10g/L of glycerol and/or butanol, 1-12g/L, N g/L of trihydroxypropyl hydroxyethyl ethylenediamine, 0.02-0.6g/L of 2-ethylhexyl sulfate sodium salt and 0.01-0.8g/L of water.
In the microetching agent, the sulfuric acid and the hydrogen peroxide have the main functions of corroding and dissolving copper or copper alloy, and the addition of the citric acid and/or the citrate can shield copper ions in the microetching liquid (the copper exists in the microetching liquid in the form of copper ions after microetching), so that the reduction of the microetching rate, poor microetching uniformity, over-quick decomposition of hydrogen peroxide and the like caused by excessive copper ions are avoided, and the service life of the microetching agent is prolonged; acetic acid and/or acetate can be adsorbed on the surface of copper or copper alloy, so that the surface flatness and brightness are improved; the addition of sulfamic acid and/or sulfamate can be matched with acetic acid and/or acetate to ensure the uniformity of copper dissolution, so that the surface of copper or copper alloy forms a mirror-like effect, and the surface brightness of the copper or copper alloy is further improved; the glycerol and/or butanol has a certain catalytic action in the microetching agent, and can improve the uniformity of the surface of copper or copper alloy subjected to microetching treatment; the trihydroxypropyl hydroxyethyl ethylenediamine, the N-methylmorpholine and the sodium 2-ethylhexyl sulfate can inhibit the decomposition of hydrogen peroxide and slow down the volatilization of the hydrogen peroxide, thereby improving the stability of the microetching agent. According to the invention, acetic acid and/or acetate, sulfamic acid and/or sulfamate, citric acid and/or citrate, glycerol and/or butanol, 2-ethylhexyl sulfate sodium salt, trihydroxy propyl ethylenediamine and N-methylmorpholine are used in a matching manner, so that the copper or copper alloy micro-etching agent with good stability, long service life and good micro-etching effect can be prepared, and the surface of copper or copper alloy treated by the micro-etching agent is smooth, uniform and good in brightness and is not easy to oxidize. The concentration of each component in the microetching agent is in the range, so that the decomposition of hydrogen peroxide can be slowed down, the consumption of hydrogen peroxide is reduced, the stability of the microetching agent is improved, and the service life of the microetching agent is prolonged.
According to a preferred embodiment of the present invention, the microetching agent includes: 30-45g/L sulfuric acid, 18-28g/L hydrogen peroxide, 3-11g/L citric acid and/or citrate, 2-4g/L acetic acid and/or acetate, 0.7-1.6g/L sulfamic acid and/or sulfamate, 5-9g/L glycerol and/or butanol, 2-10g/L, N g/L trihydroxypropyl hydroxyethyl ethylenediamine, 0.04-0.5 g/L2-ethylhexyl sulfate sodium salt, and water. Therefore, the stability of the micro-etching agent can be further improved, the service life of the micro-etching agent can be prolonged, and the micro-etching uniformity, the flatness, the brightness and the oxidation resistance of the surface of the copper or the copper alloy treated by the micro-etching agent can be improved.
According to one embodiment of the invention, the weight ratio of acetic acid and/or acetate to sulfamic acid and/or sulfamate in the microetching agent is (3-1): 1. satisfying the above relationship can further improve the micro-etching uniformity, flatness, brightness and oxidation resistance of the copper or copper alloy surface treated by the micro-etching agent.
According to one embodiment of the invention, the weight ratio of sulfuric acid to citric acid and/or citrate in the microetching agent is (10-3): 1. the decomposition of hydrogen peroxide can be further slowed down, the stability of the microetching agent is improved, and the service life of the microetching agent is prolonged.
In a second aspect of the invention, a method for preparing a copper or copper alloy microetching agent is provided, wherein sulfuric acid, hydrogen peroxide, citric acid and/or citrate, acetic acid and/or acetate, sulfamic acid and/or sulfamate, glycerol and/or butanol, trihydroxypropyl hydroxyethyl ethylenediamine, N-methylmorpholine and sodium 2-ethylhexyl sulfate in the copper or copper alloy microetching agent are dissolved in water to form the copper or copper alloy microetching agent.
According to one embodiment of the invention, the preparation method of the copper or copper alloy microetching agent comprises the following steps:
a. adding sulfuric acid into a proper amount of water, stirring and dissolving;
b. adding citric acid and/or citrate, sulfamic acid and/or sulfamate and 2-ethylhexyl sulfate sodium salt into the solution obtained in the step a, and stirring for dissolving;
c. b, adding hydrogen peroxide into the solution obtained in the step b, and stirring for dissolving;
d. and c, adding glycerol and/or butanol, trihydroxypropyl hydroxyethyl ethylenediamine and N-methylmorpholine into the solution obtained in the step c, and stirring and dissolving to obtain the microetching agent. Therefore, the microetching agent prepared by the method has good uniformity and stability.
In a third aspect of the present invention, there is provided a microetching method using the microetching agent, wherein the microetching agent is brought into contact with the surface of the copper or copper alloy substrate to perform an etching treatment.
According to one embodiment of the invention, the microetching temperature is 25-35 ℃ and the microetching time is 60-300 s. The temperature and time of the microetching are in the above range, and the microetching effect of the copper or the copper alloy can be further ensured. The microetching reaction is slow due to the excessively low temperature of the microetching; the temperature of the micro-etching is too high, and the volatilization or self-decomposition of the hydrogen peroxide is accelerated. The microetching time is too short, the microetching effect is not obvious, and the microetching time is too long, so that the waste of materials and the waste of metal and liquid medicine are caused.
The present invention is further illustrated by the following examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. All the raw materials in the examples of the present invention are commercially available products unless otherwise specified.
Example 1
Preparing a copper micro-etching agent:
a. adding sulfuric acid into a proper amount of water, stirring and dissolving;
b. adding citric acid, sulfamic acid and 2-ethylhexyl sulfate sodium salt into the solution obtained in the step a, and stirring for dissolving;
c. b, adding hydrogen peroxide into the solution obtained in the step b, and stirring for dissolving;
d. and (c) adding glycerol, trihydroxypropyl hydroxyethyl ethylenediamine and N-methylmorpholine into the solution obtained in the step (c), and stirring to dissolve to obtain a microetching agent A1. Wherein: 36g/L sulfuric acid, 22g/L hydrogen peroxide, 6g/L citric acid, 3g/L acetic acid, 1g/L sulfamic acid, 5g/L glycerol, 5g/L trihydroxypropyl hydroxyethyl ethylenediamine, 0.1g/L L, N-methyl morpholine and 0.1g/L sodium 2-ethylhexyl sulfate;
microetching copper: and contacting the surface of the copper product with the microetching agent for etching treatment, wherein the temperature of the microetching agent is 30 ℃, the microetching time is 180s, and cleaning to obtain a microetched copper product B1.
Example 2
Preparing a copper micro-etching agent:
a. adding sulfuric acid into a proper amount of water, stirring and dissolving;
b. adding citric acid, sulfamic acid and 2-ethylhexyl sulfate sodium salt into the solution obtained in the step a, and stirring for dissolving;
c. b, adding hydrogen peroxide into the solution obtained in the step b, and stirring for dissolving;
d. and (c) adding glycerol, trihydroxypropyl hydroxyethyl ethylenediamine and N-methylmorpholine into the solution obtained in the step (c), and stirring to dissolve to obtain a microetching agent A2. Wherein: 27g/L of sulfuric acid, 15g/L of hydrogen peroxide, 2g/L of citric acid, 1g/L of acetic acid, 0.4g/L of sulfamic acid, 3g/L of glycerol, 0.02g/L of trihydroxypropyl hydroxyethyl ethylenediamine, 1g/L, N-methylmorpholine and 0.01g/L of 2-ethylhexyl sulfate sodium salt;
microetching copper: and contacting the surface of the copper product with the microetching agent for etching treatment, wherein the temperature of the microetching agent is 30 ℃, the microetching time is 180s, and cleaning to obtain a microetched copper product B2.
Example 3
Preparing a copper micro-etching agent:
a. adding sulfuric acid into a proper amount of water, stirring and dissolving;
b. adding citric acid, sulfamic acid and 2-ethylhexyl sulfate sodium salt into the solution obtained in the step a, and stirring for dissolving;
c. b, adding hydrogen peroxide into the solution obtained in the step b, and stirring for dissolving;
d. and (c) adding glycerol, trihydroxypropyl hydroxyethyl ethylenediamine and N-methylmorpholine into the solution obtained in the step (c), and stirring to dissolve to obtain a microetching agent A3. Wherein: 50g/L of sulfuric acid, 30g/L of hydrogen peroxide, 14g/L of citric acid, 6g/L of acetic acid, 2g/L of sulfamic acid, 10g/L of glycerol, 12g/L, N g of trihydroxypropyl hydroxyethyl ethylenediamine-0.6 g/L of methyl morpholine and 0.8g/L of 2-ethylhexyl sulfate sodium salt;
microetching copper: and contacting the surface of the copper product with the microetching agent for etching treatment, wherein the temperature of the microetching agent is 30 ℃, the microetching time is 180s, and cleaning to obtain a microetched copper product B3.
Example 4
Preparing a copper micro-etching agent:
a. adding sulfuric acid into a proper amount of water, stirring and dissolving;
b. adding citric acid, sulfamic acid and 2-ethylhexyl sulfate sodium salt into the solution obtained in the step a, and stirring for dissolving;
c. b, adding hydrogen peroxide into the solution obtained in the step b, and stirring for dissolving;
d. and (c) adding glycerol, trihydroxypropyl hydroxyethyl ethylenediamine and N-methylmorpholine into the solution obtained in the step (c), and stirring to dissolve to obtain a microetching agent A4. Wherein: 35g/L of sulfuric acid, 23g/L of hydrogen peroxide, 9g/L of citric acid, 3g/L of acetic acid, 1.2g/L of sulfamic acid, 6g/L of glycerol, 6g/L of trihydroxypropyl hydroxyethyl ethylenediamine, 0.2g/L of L, N-methylmorpholine and 0.1g/L of 2-ethylhexyl sulfate sodium salt;
microetching copper: and contacting the surface of the copper product with the microetching agent for etching treatment, wherein the temperature of the microetching agent is 30 ℃, the microetching time is 180s, and cleaning to obtain a microetched copper product B4.
Example 5
Preparing a copper micro-etching agent:
a. adding sulfuric acid into a proper amount of water, stirring and dissolving;
b. adding citric acid, sulfamic acid and 2-ethylhexyl sulfate sodium salt into the solution obtained in the step a, and stirring for dissolving;
c. b, adding hydrogen peroxide into the solution obtained in the step b, and stirring for dissolving;
d. and (c) adding glycerol, trihydroxypropyl hydroxyethyl ethylenediamine and N-methylmorpholine into the solution obtained in the step (c), and stirring to dissolve to obtain a microetching agent A5. Wherein: 40g/L sulfuric acid, 25g/L hydrogen peroxide, 8g/L citric acid, 3g/L acetic acid, 1.2g/L sulfamic acid, 5g/L glycerol, 7g/L, N g/L trihydroxypropyl hydroxyethyl ethylenediamine-0.4 g/L methylmorpholine and 0.5g/L sodium 2-ethylhexyl sulfate;
microetching copper: and contacting the surface of the copper product with the microetching agent for etching treatment, wherein the temperature of the microetching agent is 30 ℃, the microetching time is 180s, and cleaning to obtain a microetched copper product B5.
Example 6
Preparing a copper micro-etching agent:
a. adding sulfuric acid into a proper amount of water, stirring and dissolving;
b. adding citric acid, sulfamic acid and 2-ethylhexyl sulfate sodium salt into the solution obtained in the step a, and stirring for dissolving;
c. b, adding hydrogen peroxide into the solution obtained in the step b, and stirring for dissolving;
d. and (c) adding glycerol, trihydroxypropyl hydroxyethyl ethylenediamine and N-methylmorpholine into the solution obtained in the step (c), and stirring to dissolve to obtain a microetching agent A6. Wherein: 45g/L sulfuric acid, 28g/L hydrogen peroxide, 11g/L citric acid, 4g/L acetic acid, 1.6g/L sulfamic acid, 9g/L glycerol, 10g/L, N g/L trihydroxypropyl hydroxyethyl ethylenediamine-0.5 g/L methylmorpholine and 0.7g/L sodium 2-ethylhexyl sulfate;
microetching copper: and contacting the surface of the copper product with the microetching agent for etching treatment, wherein the temperature of the microetching agent is 30 ℃, the microetching time is 180s, and cleaning to obtain a microetched copper product B6.
Example 7
Preparing a copper micro-etching agent:
a. adding sulfuric acid into a proper amount of water, stirring and dissolving;
b. adding citric acid, sulfamic acid and 2-ethylhexyl sulfate sodium salt into the solution obtained in the step a, and stirring for dissolving;
c. b, adding hydrogen peroxide into the solution obtained in the step b, and stirring for dissolving;
d. and (c) adding glycerol, trihydroxypropyl hydroxyethyl ethylenediamine and N-methylmorpholine into the solution obtained in the step (c), and stirring to dissolve to obtain a microetching agent A7. Wherein: 30g/L of sulfuric acid, 18g/L of hydrogen peroxide, 3g/L of citric acid, 2g/L of acetic acid, 0.7g/L of sulfamic acid, 5g/L of glycerol, 2g/L, N g of trihydroxypropyl hydroxyethyl ethylenediamine-0.04 g/L of methylmorpholine and 0.02g/L of 2-ethylhexyl sulfate sodium salt;
microetching copper: and contacting the surface of the copper product with the microetching agent for etching treatment, wherein the temperature of the microetching agent is 30 ℃, the microetching time is 180s, and cleaning to obtain a microetched copper product B7.
Comparative example 1
The procedure of example 1 was repeated except that the concentration of trimethylolpropane hydroxyethylethylenediamine was 20g/L to obtain a microetched copper product DB 1.
Comparative example 2
The procedure of example 1 was repeated except that the concentration of trimethylolpropane hydroxyethylethylenediamine was 0.2g/L to obtain a microetched copper product DB 2.
Comparative example 3
The procedure of example 1 was repeated except that N-methylmorpholine was used in a concentration of 2g/L to obtain a microetched copper product DB 3.
Comparative example 4
The procedure of example 1 was repeated except that the concentration of 2-ethylhexyl sulfate sodium salt was 2g/L, to obtain a microetched copper product DB 4.
Comparative example 5
A microetched copper product DB5 was produced in the same manner as in example 1, except that acetic acid and sulfamic acid were not contained.
Comparative example 6
A microetched copper product DB6 was prepared in the same manner as in example 1, except that trimethylolpropane hydroxyethylethylenediamine was not contained in the copper product.
Comparative example 7
A microetched copper product DB7 was produced in the same manner as in example 1, except that N-methylmorpholine was not contained.
Comparative example 8
A microetched copper product DB8 was produced in the same manner as in example 1, except that 2-ethylhexyl sulfate sodium salt was used.
The formulations of the microetching agents of the examples and comparative examples are shown in table 1:
performance testing and results
1. Surface appearance: visual inspection of the appearance of the microetching treated copper surface classified it into five grades of A, B, C, D, E:
a: the paint has obvious metal luster, uniform color, no darkening, flat surface, no pit and no scratch;
b: the paint has certain metal luster, uniform color, no darkening, flat surface, no pit and no scratch;
c: matte, uniform color, no darkness, flat surface, no pit and no scratch;
d: matte, uniform color, no darkness, flat surface, no pits and slight scratches;
e: the paint has certain metal luster, and parts of the paint are dark and have uneven color;
2. oxidation resistance: after the copper product is subjected to microetching, deionized water is washed, then the copper product is put into a copper protective agent for 3 minutes, the copper product is taken out, washed with ultrapure water and dried, and after the copper product is placed for 24 hours, the surface of the product is visually observed under the condition of a daylight lamp to see whether oxidized spots exist or not and a yellowish-discoloring area exists;
3. and (3) detecting the microetching amount: measuring the weight change of the copper product before and after the microetching to 0.01g, wherein the microetching amount is preferably between 0.6 and 1.5;
4. roughness: the roughness after micro-etching is detected by using a TR200 handheld roughness meter, the roughness is low, the yield of subsequent copper welding is reduced, the roughness is too high, and the surface is easy to oxidize. The roughness is preferably between 0.5 and 1.0;
5. microetching agent lifetime: the method comprises the steps of processing a copper product by using a microetching agent, and recording the number of copper products which can be processed before the service life of the microetching agent is expired (the microetching amount is less than 0.60g, namely the service life is expired) (counting by the volume of the microetching agent as 5L, analyzing the concentration of a replenishing liquid medicine to an original value every 10PCS, and ensuring that the reduction of the microetching amount is not caused by the reduction of the concentration);
6. micro-etching agent stability: the change of the hydrogen peroxide concentration of the micro-etching agent after standing for 24 hours at room temperature is less and more stable.
The test results are shown in table 2:
from the above test results, it can be seen that: the micro-etching agent prepared by the embodiment of the invention has good stability, long service life and good micro-etching effect, and the copper product treated by the micro-etching agent has good surface brightness and good oxidation resistance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. It is not necessary or necessary to exhaustively enumerate all embodiments herein, and obvious variations or modifications can be introduced thereby while remaining within the scope of the invention as claimed.
Claims (8)
1. A copper or copper alloy microetching agent, comprising:
27-50g/L sulfuric acid
15-30g/L of hydrogen peroxide
1-14 g/L of citric acid and/or citrate
Acetic acid and/or acetate 1-6 g/L
0.4-2g/L of sulfamic acid and/or sulfamate
3-10g/L of glycerol and/or butanol
1-12g/L of trihydroxypropyl hydroxyethyl ethylenediamine
0.02-0.6g/L of N-methylmorpholine
2-ethylhexyl sulfate sodium salt 0.01-0.8g/L
And water.
2. The microetching agent according to claim 1, wherein the microetching agent comprises:
sulfuric acid 30-45g/L
18-28g/L of hydrogen peroxide
3-11g/L of citric acid and/or citrate
Acetic acid and/or acetate 2-4g/L
0.7-1.6g/L of sulfamic acid and/or sulfamate
Glycerol and/or butanol 5-9g/L
2-10g/L of trihydroxypropyl hydroxyethyl ethylenediamine
0.04-0.5g/L of N-methylmorpholine
2-ethylhexyl sulfate sodium salt 0.02-0.7g/L
And water.
3. The microetching agent according to claim 1, wherein the weight ratio of acetic acid and/or acetate to sulfamic acid and/or sulfamate in the microetching agent is (3-1): 1.
4. the microetching agent according to claim 1, wherein the weight ratio of sulfuric acid to citric acid and/or citrate in the microetching agent is (10-3): 1.
5. a method for preparing a copper or copper alloy microetching agent, which is characterized in that sulfuric acid, hydrogen peroxide, citric acid and/or citrate, acetic acid and/or acetate, sulfamic acid and/or sulfamate, glycerol and/or butanol, trihydroxypropylhydroxyethylethylenediamine, N-methylmorpholine and 2-ethylhexyl sulfate sodium salt in the copper or copper alloy microetching agent according to any one of claims 1 to 4 are dissolved in water to form the copper or copper alloy microetching agent.
6. The method of claim 5, comprising the steps of:
a. adding sulfuric acid into a proper amount of water, stirring and dissolving;
b. adding citric acid and/or citrate, sulfamic acid and/or sulfamate and 2-ethylhexyl sulfate sodium salt into the solution obtained in the step a, and stirring for dissolving;
c. b, adding hydrogen peroxide into the solution obtained in the step b, and stirring for dissolving;
d. and c, adding glycerol and/or butanol, trihydroxypropyl hydroxyethyl ethylenediamine and N-methylmorpholine into the solution obtained in the step c, and stirring and dissolving to obtain the microetching agent.
7. A microetching method using the microetching agent according to any one of claims 1 to 4, wherein the surface of the copper or copper alloy substrate is subjected to an etching treatment by contacting with the microetching agent.
8. The microetching method according to claim 7, wherein the microetching temperature is 25 to 35 ℃ and the microetching time is 60 to 300 s.
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