CN112831784A - Acidic etching solution and control method for improving etching precision thereof - Google Patents
Acidic etching solution and control method for improving etching precision thereof Download PDFInfo
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- CN112831784A CN112831784A CN202011630645.5A CN202011630645A CN112831784A CN 112831784 A CN112831784 A CN 112831784A CN 202011630645 A CN202011630645 A CN 202011630645A CN 112831784 A CN112831784 A CN 112831784A
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- etching
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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 an acidic etching solution and a control method for improving the etching precision of the acidic etching solution, wherein the method comprises the following steps: placing a copper-containing product to be etched in an etching tank, and adding an acidic etching solution into the etching tank, wherein the acidic etching solution comprises divalent copper ions, hydrogen ions, an oxidizing agent and a complexing agent, and the complexing agent is ethylenediamine tetraacetic acid; in the reaction process, the concentrations of divalent copper ions, complexing agents and hydrogen ions in the etching tank are monitored in real time, the concentration of the divalent copper ions is controlled within the range of 145-155 g/L, the concentration of the hydrogen ions is controlled within the range of 0.6-1 equivalent, the concentration of the complexing agents is controlled within the range of 200-600 ppm, and the concentration of the oxidizing agents is controlled within the range of 1-5 g/L. The acid etching solution has high etching factor, stable reaction during etching and capability of improving etching precision, thereby improving etching effect; the reaction is easy to control, the stability of the reaction is ensured, and the etching precision is improved, so that the quality of the etched product is improved.
Description
Technical Field
The invention relates to the field of etching solutions, in particular to an acidic etching solution and a control method for improving etching precision of the acidic etching solution.
Background
The etching is a conventional procedure in the circuit board, redundant copper layers on the surface of the circuit board can be removed by etching, the improvement of the etching precision plays an important role in improving the quality of the circuit board, along with the rapid development of electronic technology, the requirement on the precision of the circuit board is higher and higher, and the etching process also faces unprecedented technical pressure. On the other hand, with the formation of the global competitive pattern of the PCB, the one-time production yield becomes the life line of each circuit board manufacturing enterprise, and the circuit board manufacturing enterprise with high precision can receive more high-end orders; which circuit board manufacturing enterprise's disposable yield is high, and manufacturing cost just can realize lower, and enterprise competitiveness just is stronger. The precision and one-time production yield of the circuit board are related to a plurality of production processes, wherein the etching solution can improve the production yield and the etching precision, the datamation of the etching precision is an etching factor, the larger the etching factor is, the better the etching precision is, and therefore, the improvement of the etching factor is the key for improving the etching precision. However, the conventional etching solutions are not high in etching accuracy and relatively poor in stability.
Disclosure of Invention
The invention provides an acidic etching solution and a control method for improving etching precision, aiming at solving the problems of low etching precision and poor stability of the existing etching solution.
An acidic etching solution comprises 145-155 g/L of divalent copper ions, 0.6-1 equivalent of hydrogen ions, 1-5 g/L of an oxidant and 200-600 ppm of a complexing agent, wherein the complexing agent is ethylenediamine tetraacetic acid, and the acidic etching solution is high in etching factor and stability during etching reaction.
Optionally, the concentration of the divalent copper ions is 150g/L, and the acid etching solution at the concentration has a good etching effect.
Optionally, the concentration of the hydrogen ions is 0.8 equivalent, and the acid etching solution at the concentration has a good etching effect.
Optionally, the hydrogen ions are provided by a hydrochloric acid solution, so that the cost is low.
Optionally, the oxidizing agent is sodium chlorate.
A control method for improving the etching precision of an acidic etching solution comprises the following steps:
placing a copper-containing product to be etched in an etching tank, and adding an acidic etching solution into the etching tank, wherein the acidic etching solution comprises divalent copper ions, hydrogen ions, an oxidizing agent and a complexing agent, and the complexing agent is ethylenediamine tetraacetic acid;
in the reaction process, the concentrations of divalent copper ions, complexing agents and hydrogen ions in the etching tank are monitored in real time, the concentration of the divalent copper ions is controlled within the range of 145-155 g/L, the concentration of the hydrogen ions is controlled within the range of 0.6-1 equivalent, the concentration of the complexing agents is controlled within the range of 200-600 ppm, and the concentration of the oxidizing agents is controlled within the range of 1-5 g/L. The control method has the advantages that each step is easy to operate and control, the cost can be reduced, and meanwhile, the etching precision can be improved.
Optionally, the adding of the acidic etching solution comprises the following steps: firstly, adding a solution containing divalent copper ions into an etching tank, then adding a complexing agent and an oxidizing agent, and finally adding a solution containing hydrogen ions, wherein the solution containing hydrogen ions is hydrochloric acid, and the oxidizing agent is sodium chlorate.
Optionally, the acidic etching solution is added into the etching bath in a spraying manner, so that the etching reaction is more sufficient.
Optionally, the copper-containing product is a PCB board.
Compared with the prior art, the invention has the beneficial effects that: the invention provides an acidic etching solution and a control method for improving the etching precision of the acidic etching solution, the acidic etching solution has high etching factor, the reaction is stable during etching, and the etching precision can be improved, so that the etching effect is improved; the control method for improving the etching precision of the acidic etching solution is also provided, the reaction process is easy to control, the stability of the reaction is ensured, the etching precision is improved, and thus the quality of the etched product is improved.
Detailed Description
The invention discloses an acid etching solution, and the invention is further described in detail by combining the following examples.
Example 1:
an acidic etching solution comprises bivalent copper ions with the concentration of 150g/L, 0.8 equivalent hydrogen ions, 3g/L of an oxidizing agent and a complexing agent with the concentration of 400ppm, wherein the complexing agent is ethylenediamine tetraacetic acid. In some embodiments, the hydrogen ions are provided by a hydrochloric acid solution.
The specific principle is as follows: during etching, cupric ions in the acid etching solution oxidize copper atoms to generate monovalent copper ions, sodium chlorate is used as an oxidant to oxidize the monovalent copper ions to generate the divalent copper ions, the purpose of continuous and stable production is achieved through the reciprocating circulation, and the ethylenediaminetetraacetic acid can reduce the number of free monovalent copper ions and improve the etching factor. The etching solution has good stability and can improve the etching precision.
Example 2:
an acidic etching solution comprises 145g/L of divalent copper ions, 0.6 equivalent of hydrogen ions, 1g/L of oxidant and 200ppm of complexing agent, wherein the complexing agent is ethylenediamine tetraacetic acid. In some embodiments, the hydrogen ions are provided by a hydrochloric acid solution.
The specific principle is as follows: during etching, cupric ions in the acid etching solution oxidize copper atoms to generate monovalent copper ions, sodium chlorate is used as an oxidant to oxidize the monovalent copper ions to generate the divalent copper ions, the purpose of continuous and stable production is achieved through the reciprocating circulation, and the ethylenediaminetetraacetic acid can reduce the number of free monovalent copper ions and improve the etching factor. The etching solution has good stability and can improve the etching precision.
Example 3:
an acidic etching solution comprises divalent copper ions with the concentration of 155g/L, 1 equivalent of hydrogen ions, 4g/L of an oxidizing agent and a complexing agent with the concentration of 600ppm, wherein the complexing agent is ethylene diamine tetraacetic acid. In some embodiments, the hydrogen ions are provided by a hydrochloric acid solution.
The specific principle is as follows: during etching, cupric ions in the acid etching solution oxidize copper atoms to generate monovalent copper ions, sodium chlorate is used as an oxidant to oxidize the monovalent copper ions to generate the divalent copper ions, the purpose of continuous and stable production is achieved through the reciprocating circulation, and the ethylenediaminetetraacetic acid can reduce the number of free monovalent copper ions and improve the etching factor. The etching solution has good stability and can improve the etching precision.
Example 4:
an acidic etching solution comprises 148g/L of divalent copper ions, 0.7 equivalent of hydrogen ions, 5g/L of an oxidizing agent and 500ppm of a complexing agent, wherein the complexing agent is ethylenediamine tetraacetic acid. In some embodiments, the hydrogen ions are provided by a hydrochloric acid solution.
The specific principle is as follows: during etching, cupric ions in the acid etching solution oxidize copper atoms to generate monovalent copper ions, sodium chlorate is used as an oxidant to oxidize the monovalent copper ions to generate the divalent copper ions, the purpose of continuous and stable production is achieved through the reciprocating circulation, and the ethylenediaminetetraacetic acid can reduce the number of free monovalent copper ions and improve the etching factor. The etching solution has good stability and can improve the etching precision.
The invention also discloses a control method for improving the etching precision of the acidic etching solution, and the invention is further described in detail by combining the embodiment.
Example 1:
a control method for improving the etching precision of an acidic etching solution comprises the following steps:
placing a copper-containing product to be etched in an etching tank, and adding an acidic etching solution into the etching tank, wherein the acidic etching solution comprises divalent copper ions, hydrogen ions, an oxidant and a complexing agent, and the complexing agent is ethylenediamine tetraacetic acid; the copper-containing product is a PCB or other product, and the invention is not limited thereto. The acidic etching solution is added, and the method comprises the following steps: firstly, adding a solution containing divalent copper ions into an etching tank, then adding a complexing agent and an oxidizing agent, and finally adding a solution containing hydrogen ions, wherein the solution containing hydrogen ions is hydrochloric acid, the oxidizing agent is sodium chlorate, and the acidic etching solution is added into the etching tank in a spraying manner.
In the reaction process, the concentrations of divalent copper ions, complexing agents and hydrogen ions in the etching tank are monitored in real time, the concentration of the divalent copper ions is controlled within the range of 150g/L, the concentration of the hydrogen ions is controlled within the range of 0.8 equivalent, the concentration of the complexing agents is controlled within the range of 400ppm, and the concentration of the oxidizing agents is controlled within the range of 3 g/L.
In the reaction process, the concentrations of the divalent copper ions, the complexing agent and the hydrogen ions are controlled, so that the reaction stability can be improved, and the etching precision is improved. If the concentration of the divalent copper ions is too high, copper chloride crystals can be separated out; hydrochloric acid can provide hydrogen ions, but the hydrochloric acid has strong volatility, and the hydrogen ions are controlled within a specified range, so that the stability of the etching reaction can be improved; the higher the free monovalent copper ions are, the smaller the etching factor is, and the complexing agent can reduce the number of the free monovalent copper ions, thereby improving the etching factor and the etching precision.
Example 2:
a control method for improving the etching precision of an acidic etching solution comprises the following steps:
placing a copper-containing product to be etched in an etching tank, and adding an acidic etching solution into the etching tank, wherein the acidic etching solution comprises divalent copper ions, hydrogen ions, an oxidant and a complexing agent, and the complexing agent is ethylenediamine tetraacetic acid; the copper-containing product is a PCB or other product, and the invention is not limited thereto. The acidic etching solution is added, and the method comprises the following steps: firstly, adding a solution containing divalent copper ions into an etching tank, then adding a complexing agent and an oxidizing agent, and finally adding a solution containing hydrogen ions, wherein the solution containing hydrogen ions is hydrochloric acid, the oxidizing agent is sodium chlorate, and the acidic etching solution is added into the etching tank in a spraying manner.
In the reaction process, the concentrations of divalent copper ions, complexing agents and hydrogen ions in the etching tank are monitored in real time, the concentration of the divalent copper ions is controlled within the range of 145g/L, the concentration of the hydrogen ions is controlled within the range of 0.6 equivalent, the concentration of the complexing agents is controlled within the range of 200ppm, and the concentration of the oxidizing agents is controlled within the range of 1 g/L.
In the reaction process, the concentrations of the divalent copper ions, the complexing agent and the hydrogen ions are controlled, so that the reaction stability can be improved, and the etching precision is improved. If the concentration of the divalent copper ions is too high, copper chloride crystals can be separated out; hydrochloric acid can provide hydrogen ions, but the hydrochloric acid has strong volatility, and the hydrogen ions are controlled within a specified range, so that the stability of the etching reaction can be improved; the higher the free monovalent copper ions are, the smaller the etching factor is, and the complexing agent can reduce the number of the free monovalent copper ions, thereby improving the etching factor and the etching precision.
Example 3:
a control method for improving the etching precision of an acidic etching solution comprises the following steps:
placing a copper-containing product to be etched in an etching tank, and adding an acidic etching solution into the etching tank, wherein the acidic etching solution comprises divalent copper ions, hydrogen ions, an oxidant and a complexing agent, and the complexing agent is ethylenediamine tetraacetic acid; the copper-containing product is a PCB or other product, and the invention is not limited thereto. The acidic etching solution is added, and the method comprises the following steps: firstly, adding a solution containing divalent copper ions into an etching tank, then adding a complexing agent and an oxidizing agent, and finally adding a solution containing hydrogen ions, wherein the solution containing hydrogen ions is hydrochloric acid, the oxidizing agent is sodium chlorate, and the acidic etching solution is added into the etching tank in a spraying manner.
In the reaction process, the concentrations of divalent copper ions, complexing agents and hydrogen ions in the etching tank are monitored in real time, the concentration of the divalent copper ions is controlled within the range of 155g/L, the concentration of the hydrogen ions is controlled within the range of 1 equivalent, the concentration of the complexing agents is controlled within the range of 600ppm, and the concentration of the oxidizing agents is controlled within the range of 4 g/L.
In the reaction process, the concentrations of the divalent copper ions, the complexing agent and the hydrogen ions are controlled, so that the reaction stability can be improved, and the etching precision is improved. If the concentration of the divalent copper ions is too high, copper chloride crystals can be separated out; hydrochloric acid can provide hydrogen ions, but the hydrochloric acid has strong volatility, and the hydrogen ions are controlled within a specified range, so that the stability of the etching reaction can be improved; the higher the free monovalent copper ions are, the smaller the etching factor is, and the complexing agent can reduce the number of the free monovalent copper ions, thereby improving the etching factor and the etching precision.
Example 4:
a control method for improving the etching precision of an acidic etching solution comprises the following steps:
placing a copper-containing product to be etched in an etching tank, and adding an acidic etching solution into the etching tank, wherein the acidic etching solution comprises divalent copper ions, hydrogen ions, an oxidant and a complexing agent, and the complexing agent is ethylenediamine tetraacetic acid; the copper-containing product is a PCB or other product, and the invention is not limited thereto. The acidic etching solution is added, and the method comprises the following steps: firstly, adding a solution containing divalent copper ions into an etching tank, then adding a complexing agent and an oxidizing agent, and finally adding a solution containing hydrogen ions, wherein the solution containing hydrogen ions is hydrochloric acid, the oxidizing agent is sodium chlorate, and the acidic etching solution is added into the etching tank in a spraying manner.
In the reaction process, the concentrations of divalent copper ions, complexing agents and hydrogen ions in the etching tank are monitored in real time, the concentration of the divalent copper ions is controlled within the range of 148g/L, the concentration of the hydrogen ions is controlled within the range of 0.7 equivalent, the concentration of the complexing agents is controlled within the range of 500ppm, and the concentration of the oxidizing agents is controlled within the range of 5 g/L.
In the reaction process, the concentrations of the divalent copper ions, the complexing agent and the hydrogen ions are controlled, so that the reaction stability can be improved, and the etching precision is improved. If the concentration of the divalent copper ions is too high, copper chloride crystals can be separated out; hydrochloric acid can provide hydrogen ions, but the hydrochloric acid has strong volatility, and the hydrogen ions are controlled within a specified range, so that the stability of the etching reaction can be improved; the higher the free monovalent copper ions are, the smaller the etching factor is, and the complexing agent can reduce the number of the free monovalent copper ions, thereby improving the etching factor and the etching precision.
The invention provides an acidic etching solution and a control method for improving the etching precision of the acidic etching solution, the acidic etching solution has high etching factor, the reaction is stable during etching, and the etching precision can be improved, so that the etching effect is improved; the control method for improving the etching precision of the acidic etching solution is also provided, the reaction process is easy to control, the stability of the reaction is ensured, the etching precision is improved, and thus the quality of the etched product is improved.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (9)
1. An acidic etching solution, characterized in that: the copper ion complexing agent comprises 145-155 g/L of divalent copper ions, 0.6-1 equivalent of hydrogen ions, 1-5 g/L of an oxidizing agent and 200-600 ppm of complexing agent, wherein the complexing agent is ethylenediamine tetraacetic acid.
2. The acidic etchant according to claim 1, wherein: the concentration of the divalent copper ions is 150 g/L.
3. The acidic etchant according to claim 1, wherein: the concentration of the hydrogen ions was 0.8 equivalents.
4. An acidic etching solution according to claim 1 or 3, characterized in that: the hydrogen ions are provided by a hydrochloric acid solution.
5. The acidic etchant according to claim 1, wherein: the oxidant is sodium chlorate.
6. A control method for improving the etching precision of acidic etching solution is characterized in that: the method comprises the following steps:
placing a copper-containing product to be etched in an etching tank, and adding an acidic etching solution into the etching tank, wherein the acidic etching solution comprises divalent copper ions, hydrogen ions, an oxidizing agent and a complexing agent, and the complexing agent is ethylenediamine tetraacetic acid;
in the reaction process, the concentrations of divalent copper ions, complexing agents and hydrogen ions in the etching tank are monitored in real time, the concentration of the divalent copper ions is controlled within the range of 145-155 g/L, the concentration of the hydrogen ions is controlled within the range of 0.6-1 equivalent, the concentration of the complexing agents is controlled within the range of 200-600 ppm, and the concentration of the oxidizing agents is controlled within the range of 1-5 g/L.
7. The control method for improving the etching precision of the acidic etching solution as claimed in claim 5, wherein: the acidic etching solution is added, and the method comprises the following steps:
firstly, adding a solution containing divalent copper ions into an etching tank, then adding a complexing agent and an oxidizing agent, and finally adding a solution containing hydrogen ions, wherein the solution containing hydrogen ions is hydrochloric acid, and the oxidizing agent is sodium chlorate.
8. The control method for improving the etching precision of the acidic etching solution as claimed in claim 5, wherein: the acidic etching solution is added into the etching tank in a spraying mode.
9. The control method for improving the etching precision of the acidic etching solution as claimed in claim 5, wherein: the copper-containing product is a PCB.
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| CN202011630645.5A CN112831784A (en) | 2020-12-31 | 2020-12-31 | Acidic etching solution and control method for improving etching precision thereof |
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| CN202011630645.5A CN112831784A (en) | 2020-12-31 | 2020-12-31 | Acidic etching solution and control method for improving etching precision thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139714A (en) * | 2007-10-18 | 2008-03-12 | 珠海顺泽电子实业有限公司 | Copper etching liquid composition and production method thereof |
| CN101688315A (en) * | 2007-07-11 | 2010-03-31 | 西格玛工程集团 | A method for etching copper and recovery of the spent etching solution |
| CN102154646A (en) * | 2011-03-04 | 2011-08-17 | 侯延辉 | Acidic etching solution not generating chlorine and catalyst of acidic etching solution |
| CN102634801A (en) * | 2012-04-27 | 2012-08-15 | 东莞市广华化工有限公司 | Low-acidity acidic etching regenerant and acidic etching mother liquor thereof |
| CN110453223A (en) * | 2018-05-07 | 2019-11-15 | 惠州市鸿宇泰科技有限公司 | A kind of high-effect environment-friendly type acidic etching liquid and its engraving method |
-
2020
- 2020-12-31 CN CN202011630645.5A patent/CN112831784A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101688315A (en) * | 2007-07-11 | 2010-03-31 | 西格玛工程集团 | A method for etching copper and recovery of the spent etching solution |
| CN101139714A (en) * | 2007-10-18 | 2008-03-12 | 珠海顺泽电子实业有限公司 | Copper etching liquid composition and production method thereof |
| CN102154646A (en) * | 2011-03-04 | 2011-08-17 | 侯延辉 | Acidic etching solution not generating chlorine and catalyst of acidic etching solution |
| CN102634801A (en) * | 2012-04-27 | 2012-08-15 | 东莞市广华化工有限公司 | Low-acidity acidic etching regenerant and acidic etching mother liquor thereof |
| CN110453223A (en) * | 2018-05-07 | 2019-11-15 | 惠州市鸿宇泰科技有限公司 | A kind of high-effect environment-friendly type acidic etching liquid and its engraving method |
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Application publication date: 20210525 |