CN111945163A - Copper etching liquid composition - Google Patents
Copper etching liquid composition Download PDFInfo
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- CN111945163A CN111945163A CN202010769153.8A CN202010769153A CN111945163A CN 111945163 A CN111945163 A CN 111945163A CN 202010769153 A CN202010769153 A CN 202010769153A CN 111945163 A CN111945163 A CN 111945163A
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- Prior art keywords
- acid
- etching liquid
- copper
- deionized water
- copper 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention provides a copper etching liquid composition, which comprises hydrogen peroxide, organic acid, a complexing agent, methanesulfonic acid and deionized water, wherein the copper etching liquid in the current market mainly comprises hydrogen peroxide, sulfuric acid and deionized water, the etching speed is high in the etching process of the etching liquid, the speed is difficult to control, and generated copper ions can accelerate the decomposition of hydrogen peroxide, so that the service life of the etching liquid is shortened, and meanwhile, the temperature of the liquid in the manufacturing process rises sharply, so that safety accidents are easy to happen.
Description
Technical Field
The invention relates to the field of copper etching liquid compositions, in particular to a copper etching liquid composition.
Background
In recent years, due to the rapid development of industries such as semiconductors, display panels and the like, electronic chemicals are in vigorous demand and have higher requirements on quality, and etching technology is used as an indispensable process link of semiconductors, display panels and the like, and is continuously developed and advanced, wherein wet etching is used as the most effective, most stable and most extensive etching technology by the industry for a long time, and metal copper has more excellent electrical conductivity and is widely used as a metal interconnection line, so that most of the current etching is developed around copper or copper alloy, the copper etching liquid on the market at present mainly comprises hydrogen peroxide, sulfuric acid and deionized water, in the etching process of the etching liquid, copper oxide formed by the reaction of the hydrogen peroxide and the metal copper reacts with the generated copper oxide to generate soluble divalent copper ions, and the divalent copper ions generated in the etching process can continuously oxidize the metal copper to generate monovalent copper ions due to the oxidation of the copper ions, with the continuous accumulation of copper ions in the etching solution, the etching rate is faster and becomes uncontrollable; on the other hand, copper ions accelerate the decomposition of hydrogen peroxide, thereby shortening the service life of the etching solution, and the temperature of the solution in the process is sharply increased, thereby easily causing safety accidents.
Disclosure of Invention
The invention aims to: in order to solve the problems, the copper etching solution composition is provided, and comprises hydrogen peroxide, organic acid, a complexing agent, methanesulfonic acid and deionized water,
the copper etching liquid composition comprises the following components in percentage by weight:
the balance being deionized water.
The organic acid is one of acetic acid, butyric acid, citric acid, formic acid, oxalic acid, salicylic acid and benzoic acid.
The complexing agent is one of ethylene diamine tetraacetic acid sodium salt, sulfosalicylic acid, tartaric acid and sodium citrate.
The metal ion content of the deionized water of the etching solution is less than 100 ppt.
Compared with the prior art, the invention has the beneficial effects that: in the invention, through adding a certain proportion of ethylenediamine tetraacetic acid sodium salt and methanesulfonic acid, complexing with copper ions and stabilizing the pH value of the etching solution, the service life of the etching solution is effectively prolonged, the etching rate and stability are improved, and in addition, the stable and efficient preparation method of the copper etching solution has the process advantages of few components, simple preparation and the like.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A copper etching solution composition comprises: the copper etching solution is composed of hydrogen peroxide, citric acid, ethylene diamine tetraacetic acid sodium salt, methanesulfonic acid and deionized water, and the composition comprises the following components in percentage by weight:
the rest is deionized water.
The preparation method comprises the following specific steps:
the first step is that the copper etching solution in total weight is respectively called as 20 percent of hydrogen peroxide, 10 percent of citric acid, 10 percent of ethylene diamine tetraacetic acid sodium salt, 10 percent of methanesulfonic acid and the balance of deionized water.
And secondly, adding the weighed ethylene diamine tetraacetic acid sodium salt, methanesulfonic acid and deionized water into a beaker, and stirring to dissolve.
And thirdly, adding the weighed citric acid into a beaker, and uniformly stirring.
Fourthly, adding the weighed hydrogen peroxide into a beaker, and uniformly stirring for later use.
Example 2
A copper etching solution composition comprises: the copper etching solution is composed of hydrogen peroxide, citric acid, ethylene diamine tetraacetic acid sodium salt, methanesulfonic acid and deionized water, and the composition comprises the following components in percentage by weight:
the rest is deionized water.
The preparation method comprises the following specific steps:
firstly, respectively weighing 10% of hydrogen peroxide, 5% of citric acid, 5% of ethylene diamine tetraacetic acid sodium salt, 5% of methanesulfonic acid and the balance of deionized water according to the total weight of the copper etching solution.
And secondly, adding the weighed ethylene diamine tetraacetic acid sodium salt, methanesulfonic acid and deionized water into a beaker, and stirring to dissolve.
And thirdly, adding the weighed citric acid into a beaker, and uniformly stirring.
Fourthly, adding the weighed hydrogen peroxide into a beaker, and uniformly stirring for later use.
Example 3
A copper etching solution composition comprises: the copper etching solution is composed of hydrogen peroxide, citric acid, ethylene diamine tetraacetic acid sodium salt, methanesulfonic acid and deionized water, and the composition comprises the following components in percentage by weight:
the rest is deionized water.
The preparation method comprises the following specific steps:
in the first step, the copper etching solution is respectively named as 5 percent of hydrogen peroxide, 2.5 percent of citric acid, 2.5 percent of ethylene diamine tetraacetic acid sodium salt, 2.5 percent of methanesulfonic acid and the balance of deionized water according to the total weight.
Secondly, adding the weighed ethylene diamine tetraacetic acid sodium salt, the methanesulfonic acid and the deionized water into a beaker, and stirring to dissolve
And thirdly, adding the weighed citric acid into a beaker, and uniformly stirring.
Fourthly, adding the weighed hydrogen peroxide into a beaker, and uniformly stirring for later use.
Example 4
A copper etching solution composition comprises: the copper etching solution is composed of hydrogen peroxide, citric acid, ethylene diamine tetraacetic acid sodium salt, methanesulfonic acid and deionized water, and the composition comprises the following components in percentage by weight:
the rest is deionized water.
The preparation method comprises the following specific steps:
firstly, the copper etching solution is respectively called 2.5 percent of hydrogen peroxide, 1.25 percent of citric acid, 1.25 percent of ethylene diamine tetraacetic acid sodium salt, 1.25 percent of methanesulfonic acid and the balance of deionized water according to the total weight.
Secondly, adding the weighed ethylene diamine tetraacetic acid sodium salt, the methanesulfonic acid and the deionized water into a beaker, and stirring to dissolve
And thirdly, adding the weighed citric acid into a beaker, and uniformly stirring.
Fourthly, adding the weighed hydrogen peroxide into a beaker, and uniformly stirring for later use.
Example 4
A copper etching solution composition comprises: the copper etching solution is composed of hydrogen peroxide, citric acid, ethylene diamine tetraacetic acid sodium salt, methanesulfonic acid and deionized water, and the composition comprises the following components in percentage by weight:
the rest is deionized water.
The preparation method comprises the following specific steps:
firstly, the copper etching solution is respectively called 1 percent of hydrogen peroxide, 0.5 percent of citric acid, 0.5 percent of ethylene diamine tetraacetic acid sodium salt, 0.5 percent of methanesulfonic acid and the balance of deionized water according to the total weight.
And secondly, adding the weighed ethylene diamine tetraacetic acid sodium salt, methanesulfonic acid and deionized water into a beaker, and stirring to dissolve.
And thirdly, adding the weighed citric acid into a beaker, and uniformly stirring.
Fourthly, adding the weighed hydrogen peroxide into a beaker, and uniformly stirring for later use.
And (3) performance testing:
and (3) carrying out an etching experiment on the metal copper by using the prepared copper etching solution at the temperature of 35 ℃, recording the time required for etching away the copper with a certain thickness, and calculating the etching rate. And simultaneously, observing the appearance of the cross section of the etched structural sheet by using an electron microscope, and recording the etching cone angle.
The results of etch rate and etch taper angle, etc., are in the following table:
the etching solution provided by the invention has good stability, and can provide excellent copper loading capacity (more than 10 Kpm). As can be seen from the table, the etching solution has the characteristics of higher etching rate, good etching uniformity, large etching cone angle and the like, and can be used for the manufacturing process of high-fine wires.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. Furthermore, it should be understood that although the present specification describes embodiments, this does not include only one embodiment, and such description is for clarity only, and those skilled in the art should be able to make the specification as a whole, and the embodiments may be appropriately combined to form other embodiments understood by those skilled in the art.
Claims (5)
1. The copper etching liquid composition is characterized by comprising hydrogen peroxide, organic acid, a complexing agent, methanesulfonic acid and deionized water.
2. The copper etching liquid composition according to claim 1, wherein: the copper etching liquid composition comprises the following components in percentage by weight:
3. the copper etching liquid composition according to claim 1, wherein: the organic acid is one of acetic acid, butyric acid, citric acid, formic acid, oxalic acid, salicylic acid and benzoic acid.
4. The copper etching liquid composition according to claim 1, wherein: the complexing agent is one of ethylene diamine tetraacetic acid sodium salt, sulfosalicylic acid, tartaric acid and sodium citrate.
5. The copper etching liquid composition according to claim 1, wherein: the metal ion content of the deionized water of the etching solution is less than 100 ppt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010769153.8A CN111945163A (en) | 2020-08-03 | 2020-08-03 | Copper etching liquid composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010769153.8A CN111945163A (en) | 2020-08-03 | 2020-08-03 | Copper etching liquid composition |
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| CN111945163A true CN111945163A (en) | 2020-11-17 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050056616A1 (en) * | 2003-09-17 | 2005-03-17 | International Business Machines Corporation | Method for isotropic etching of copper |
| CN101748408A (en) * | 2008-12-11 | 2010-06-23 | 长沙铂鲨环保设备有限公司 | Acidic copper dissolution solution |
| CN103526206A (en) * | 2012-07-03 | 2014-01-22 | 株式会社东进世美肯 | Metal wiring etching solution and metal wiring forming method using same |
| WO2014098392A1 (en) * | 2012-12-18 | 2014-06-26 | 주식회사 동진쎄미켐 | Metal-film etching-solution composition and etching method using same |
| CN109280919A (en) * | 2017-07-20 | 2019-01-29 | 添鸿科技股份有限公司 | The etchant constituent of copper-containing metal |
| CN110499509A (en) * | 2019-10-10 | 2019-11-26 | 昆山成功环保科技有限公司 | Copper seed etching solution for wafer-level packaging |
-
2020
- 2020-08-03 CN CN202010769153.8A patent/CN111945163A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050056616A1 (en) * | 2003-09-17 | 2005-03-17 | International Business Machines Corporation | Method for isotropic etching of copper |
| CN101748408A (en) * | 2008-12-11 | 2010-06-23 | 长沙铂鲨环保设备有限公司 | Acidic copper dissolution solution |
| CN103526206A (en) * | 2012-07-03 | 2014-01-22 | 株式会社东进世美肯 | Metal wiring etching solution and metal wiring forming method using same |
| WO2014098392A1 (en) * | 2012-12-18 | 2014-06-26 | 주식회사 동진쎄미켐 | Metal-film etching-solution composition and etching method using same |
| CN109280919A (en) * | 2017-07-20 | 2019-01-29 | 添鸿科技股份有限公司 | The etchant constituent of copper-containing metal |
| CN110499509A (en) * | 2019-10-10 | 2019-11-26 | 昆山成功环保科技有限公司 | Copper seed etching solution for wafer-level packaging |
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Application publication date: 20201117 |