A copper etching solution composition that reduces copper corrosion and etch mottling after strip water wash

Abstract

This invention provides a copper etching solution composition that reduces copper corrosion and etching crystallization after stripping and washing. The invention relates to a copper etching solution composition formulated using hydrogen peroxide, sulfuric acid, ethylenediaminetetramethylenephosphonic acid, acetone oxime, glycolic acid, phosphoric acid, L-malic acid, 1,2,3,4,5-pentahydroxyhexanoic acid, polyvinyl alcohol, and pure water. During the copper etching process, the Cu in the copper etching solution composition of this invention... 2+ Will with O 2‑ The reaction produces black CuO. When the solution reaches saturation, a black precipitate will form. Simultaneously, the copper etching solution will crystallize upon concentration. The copper etching solution composition of this invention has strong chelating ability and can reduce the Cu content in the solution. 2+ Reduces CuO production; ethylenediaminetetramethylenephosphonic acid (EDTA) acts as a chelating agent, effectively chelating Cu in solution. 2+ Content; acetone oxime effectively removes free oxygen. The copper etching solution composition of this invention can reduce crystal buildup and prevent pipe blockage.

Description

Technical Field

[0001] This invention provides a copper etching solution composition that reduces copper corrosion and etching crystallization after stripping and washing, belonging to the field of copper etching solution processing. Background Technology

[0002] In the TFT array manufacturing process, end customers face varying degrees of metal line corrosion risk during the stripping and washing process after etching. This is generally addressed by improving the performance of the stripping solution. Often, different manufacturers use different types of stripping solutions. For example, sometimes the same manufacturer may use different types of organic and water-based stripping solutions simultaneously, resulting in different metal line corrosion conditions. It is difficult to switch solutions when using them on the same platform, and even when switching solutions, a long period of testing and adjustment is required. At the same time, crystallization is prone to occur during the use of copper etching solution equipment. Crystallization is mainly caused by the formation of copper oxide and the drying of components in the copper etching solution. The formation of crystals can easily cause scratches.

[0003] For example, in patent CN107195635B, the thin-film transistor array substrate and its fabrication method, the process steps are generally divided into film formation, photoresist coating, exposure, development, etching, and stripping. After the copper etching solution etches the metal layer, the remaining photoresist is stripped by a stripping solution. During the stripping process, amines in the stripping solution easily react with copper to form self-corrosion. Organic stripping solutions are more prone to corrosion than aqueous stripping solutions, both posing varying degrees of risk of corroding the copper substrate.

[0004] Patents CN104570629B and CN107037698B respectively use water-based stripping solutions and organic-based stripping solutions to improve the corrosion problem after stripping. Because water washing is required after stripping, amine substances mixed with water will continue to generate hydroxide ions, which will adhere to the surface of the metal wire and cause corrosion to the metal wire.

[0005] This invention develops a copper etching solution composition that reduces corrosion of metal wires during the stripping and rinsing process after use, and increases the protection of metal wires during subsequent stripping and rinsing processes; at the same time, it reduces the formation of crystals in the equipment pipelines during the use of the copper etching solution equipment. Summary of the Invention

[0006] In view of this, the purpose of the present invention is to provide a copper etching solution composition that reduces corrosion of metal wires during the stripping and rinsing process after use, and increases the protection of metal wires during subsequent stripping and rinsing processes; at the same time, it reduces the formation of crystals in the equipment pipelines during the use of the copper etching solution equipment.

[0007] This invention is mainly achieved using the following technical solutions: A copper etching solution composition for reducing copper corrosion and etching crystallization after stripping and washing, the copper etching solution composition containing the following raw materials at the following concentrations: Hydrogen peroxide 110.0 g / L~150.0 g / L, sulfuric acid 50.0 g / L~60.0 g / L, ethylenediaminetetramethylenephosphonic acid 20.0 g / L~30.0 g / L, acetone oxime 2.0 g / L~3.0 g / L, glycolic acid 10.0 g / L~20.0 g / L, phosphoric acid 25.0 g / L~30.0 g / L, L-malic acid 1.0 g / L~3.0% g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 2.0 g / L~5.0 g / L, polyvinyl alcohol 5.0 g / L~10.0 g / L, the remainder is made up with pure water.

[0008] Preferably, the mass concentration of ethylenediaminetetramethylenephosphonic acid in the copper etching solution composition of the present invention, which reduces copper corrosion and etching crystallization after stripping and washing, is 10 times that of acetone oxime.

[0009] In some embodiments, a copper etching solution composition for reducing copper corrosion and etching crystallization after stripping and washing contains the following raw materials at the following concentrations: hydrogen peroxide 125 g / L, sulfuric acid 55 g / L, ethylenediaminetetramethylenephosphonic acid 25 g / L, acetone oxime 2.5 g / L, glycolic acid 15 g / L, phosphoric acid 28.5 g / L, L-malic acid 2.0 g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 3.0 g / L, polyvinyl alcohol 7.8 g / L, with the remainder made up with pure water.

[0010] In some embodiments, a copper etching solution composition for reducing copper corrosion and etching crystallization after stripping and washing contains the following raw materials at the following concentrations: hydrogen peroxide 140 g / L, sulfuric acid 50 g / L, ethylenediaminetetramethylenephosphonic acid 30 g / L, acetone oxime 2.0 g / L, glycolic acid 15 g / L, phosphoric acid 25 g / L, L-malic acid 1.0 g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 4.0 g / L, polyvinyl alcohol 5.0 g / L, with the remainder made up with pure water.

[0011] In some embodiments, a copper etching solution composition for reducing copper corrosion and etching crystallization after stripping and washing contains the following raw materials at the following concentrations: 130 g / L hydrogen peroxide, 60 g / L sulfuric acid, 20 g / L ethylenediaminetetramethylenephosphonic acid, 3.0 g / L acetone oxime, 10.0 g / L glycolic acid, 30.0 g / L phosphoric acid, 3.0 g / L L-malic acid, 2.0 g / L 1,2,3,4,5-pentahydroxyhexanoic acid, 10.0 g / L polyvinyl alcohol, with the remainder made up with pure water.

[0012] In some embodiments, a copper etching solution composition for reducing copper corrosion and etching crystallization after stripping and washing contains the following raw materials at the following concentrations: hydrogen peroxide 115.0 g / L, sulfuric acid 52 g / L, ethylenediaminetetramethylenephosphonic acid 25 g / L, acetone oxime 2.8 g / L, glycolic acid 13.5 g / L, phosphoric acid 26.5 g / L, L-malic acid 2.5 g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 4.5 g / L, polyvinyl alcohol 7.2 g / L, with the remainder made up with pure water.

[0013] In some embodiments, a copper etching solution composition for reducing copper corrosion and etching crystallization after stripping and washing contains the following raw materials at the following concentrations: hydrogen peroxide 110.0 g / L, sulfuric acid 58 g / L, ethylenediaminetetramethylenephosphonic acid 20 g / L, acetone oxime 3.0 g / L, glycolic acid 20.0 g / L, phosphoric acid 30.0 g / L, L-malic acid 1.0 g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 5.0 g / L, polyvinyl alcohol 5.0 g / L, with the remainder made up with pure water.

[0014] In some embodiments, a copper etching solution composition for reducing copper corrosion and etching crystallization after stripping and washing contains the following raw materials at the following concentrations: hydrogen peroxide 150.0 g / L, sulfuric acid 51 g / L, ethylenediaminetetramethylenephosphonic acid 22 g / L, acetone oxime 2.5 g / L, glycolic acid 10.0 g / L, phosphoric acid 26 g / L, L-malic acid 1.0 g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 3.5 g / L, polyvinyl alcohol 5.0 g / L, with the remainder made up with pure water.

[0015] Compared with existing technologies, this invention provides a copper etching solution composition that reduces copper corrosion and etching crystallization after stripping and washing. Specifically, it is prepared using hydrogen peroxide, sulfuric acid, ethylenediaminetetramethylenephosphonic acid, acetone oxime, glycolic acid, phosphoric acid, L-malic acid, 1,2,3,4,5-pentahydroxyhexanoic acid, polyvinyl alcohol, and pure water. During the copper etching process, the Cu in the copper etching solution composition of this invention... 2+ Will with O 2- The reaction produces black CuO. When the solution reaches saturation, a black precipitate will form. Simultaneously, the copper etching solution will crystallize upon concentration. The copper etching solution composition of this invention has strong chelating ability and can reduce the Cu content in the solution. 2+ Reduces CuO production; ethylenediaminetetramethylenephosphonic acid (EDTA) acts as a chelating agent, effectively chelating Cu in solution. 2+ Content; acetone oxime effectively removes free oxygen. The copper etching solution composition of this invention can reduce crystal buildup and prevent pipe blockage. Attached Figure Description

[0016] Figure 1 Images showing the results of etching a copper substrate using the copper etching solution composition of Example 1; Figure 2 Images showing the results of etching a copper substrate using the copper etching solution composition of Example 2; Figure 3 Images showing the results of etching a copper substrate using the copper etching solution composition of Comparative Example 1. Figure 4 Images showing the results of etching a copper substrate using the copper etching solution composition of Comparative Example 2. Figure 5 Images showing the results of etching a copper substrate using the copper etching solution composition of Comparative Example 3. Figure 6 Images showing the results of etching a copper substrate using the copper etching solution composition of Example 3; Figure 7 Images showing the results of etching a copper substrate using the copper etching solution composition of Example 4; Figure 8 Images showing the results of etching a copper substrate using the copper etching solution composition of Example 5; Figure 9 This is an image showing the result of etching a copper substrate using the copper etching solution composition of Example 6. Detailed Implementation

[0017] To make the objectives, technical solutions, and advantages of this invention clearer, the preferred embodiments of this invention will be described in further detail below with reference to the examples. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without inventive effort are within the scope of protection of this invention.

[0018] Example 1 This embodiment provides a copper etching solution composition that reduces copper corrosion and etching crystallization after stripping and washing, specifically containing the following concentrations of raw materials: Hydrogen peroxide 125 g / L, sulfuric acid 55 g / L, ethylenediaminetetramethylenephosphonic acid 25 g / L, acetone oxime 2.5 g / L, glycolic acid 15 g / L, phosphoric acid 28.5 g / L, L-malic acid 2.0 g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 3.0 g / L, polyvinyl alcohol 7.8 g / L, with the remainder made up with pure water.

[0019] Example 2 This embodiment provides a copper etching solution composition that reduces copper corrosion and etching crystallization after stripping and washing, specifically containing the following concentrations of raw materials: Hydrogen peroxide 140 g / L, sulfuric acid 50 g / L, ethylenediaminetetramethylenephosphonic acid 30 g / L, acetone oxime 2.0 g / L, glycolic acid 15 g / L, phosphoric acid 25 g / L, L-malic acid 1.0 g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 4.0 g / L, polyvinyl alcohol 5.0 g / L, with the remainder made up with pure water.

[0020] Example 3 This embodiment provides a copper etching solution composition that reduces copper corrosion and etching crystallization after stripping and washing, specifically containing the following concentrations of raw materials: Hydrogen peroxide 130 g / L, sulfuric acid 60 g / L, ethylenediaminetetramethylenephosphonic acid 20 g / L, acetone oxime 3.0 g / L, glycolic acid 10.0 g / L, phosphoric acid 30.0 g / L, L-malic acid 3.0 g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 2.0 g / L, polyvinyl alcohol 10.0 g / L, with the remainder made up with pure water.

[0021] Example 4 This embodiment provides a copper etching solution composition that reduces copper corrosion and etching crystallization after stripping and washing, specifically containing the following concentrations of raw materials: Hydrogen peroxide 115.0 g / L, sulfuric acid 52 g / L, ethylenediaminetetramethylenephosphonic acid 25 g / L, acetone oxime 2.8 g / L, glycolic acid 13.5 g / L, phosphoric acid 26.5 g / L, L-malic acid 2.5 g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 4.5 g / L, polyvinyl alcohol 7.2 g / L, with the remainder made up with pure water.

[0022] Example 5 This embodiment provides a copper etching solution composition that reduces copper corrosion and etching crystallization after stripping and washing, specifically containing the following concentrations of raw materials: Hydrogen peroxide 110.0 g / L, sulfuric acid 58 g / L, ethylenediaminetetramethylenephosphonic acid 20 g / L, acetone oxime 3.0 g / L, glycolic acid 20.0 g / L, phosphoric acid 30.0 g / L, L-malic acid 1.0 g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 5.0 g / L, polyvinyl alcohol 5.0 g / L, with the remainder made up with pure water.

[0023] Example 6 This embodiment provides a copper etching solution composition that reduces copper corrosion and etching crystallization after stripping and washing, specifically containing the following concentrations of raw materials: Hydrogen peroxide 150.0 g / L, sulfuric acid 51 g / L, ethylenediaminetetramethylenephosphonic acid 22 g / L, acetone oxime 2.5 g / L, glycolic acid 10.0 g / L, phosphoric acid 26 g / L, L-malic acid 1.0 g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 3.5 g / L, polyvinyl alcohol 5.0 g / L, with the remainder made up with pure water.

[0024] Comparative Example 1 A copper etching solution composition, specifically containing the following concentrations of raw materials: Hydrogen peroxide 125 g / L, sulfuric acid 55 g / L, ethylenediaminetetramethylenephosphonic acid 25 g / L, acetone oxime 2.5 g / L, glycolic acid 15 g / L, phosphoric acid 28.5 g / L, L-malic acid 2.0 g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 3.0 g / L, with the remainder made up with pure water.

[0025] Comparative Example 2 A copper etching solution composition, specifically containing the following concentrations of raw materials: Hydrogen peroxide 140 g / L, sulfuric acid 50 g / L, ethylenediaminetetramethylenephosphonic acid 10 g / L, acetone oxime 2.0 g / L, glycolic acid 15 g / L, phosphoric acid 25 g / L, L-malic acid 1.0 g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 4.0 g / L, polyvinyl alcohol 5.0 g / L, with the remainder made up with pure water.

[0026] Comparative Example 3 A copper etching solution composition, specifically containing the following concentrations of raw materials: Hydrogen peroxide 130 g / L, sulfuric acid 60 g / L, ethylenediaminetetramethylenephosphonic acid 20 g / L, acetone oxime 1.0 g / L, glycolic acid 10.0 g / L, phosphoric acid 30.0 g / L, L-malic acid 3.0 g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 2.0 g / L, polyvinyl alcohol 10.0 g / L, with the remainder made up with pure water.

[0027] Experiments were conducted using the copper etching solution compositions prepared in Examples 1-6 and Comparative Examples 1-3 of the present invention.

[0028] Specific experimental procedure: 3000 ppm copper powder was added to the above etching solution composition and stirred until the copper powder was completely dissolved. After the copper powder was dissolved, the copper substrate was placed in the etching solution composition for etching tests, with an etching time of 120 seconds for each test. The etching test temperature was 30℃, and the peeling test temperature was 45℃. The crystallization amount was tested using 0.2 μm PTFE filter paper under vacuum. All copper substrates used were copper film substrates with a copper film thickness of 650 nm.

[0029]

[0030] As can be seen from Table 1, the copper etching solution composition of Comparative Example 1, which did not contain polyvinyl alcohol, exhibited severe corrosion after etching the copper substrate. The copper etching solution composition of Comparative Example 2, which reduced the content of ethylenediaminetetramethylenephosphonic acid, and Comparative Example 3, which reduced the content of acetone oxime, exhibited slight corrosion after etching the copper substrate.

[0031] The embodiments described above are some, but not all, embodiments of the present invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

Claims

1. A copper etching solution composition for reducing copper corrosion and etching crystallization after stripping and washing, characterized in that, The copper etching solution composition contains the following concentrations of raw materials: Hydrogen peroxide 110.0g / L~150.0g / L, sulfuric acid 50.0g / L~60.0g / L, ethylenediaminetetramethylenephosphonic acid 20.0g / L~30.0g / L, acetone oxime 2.0g / L~3.0g / L, glycolic acid 10.0g / L~20.0g / L, phosphoric acid 25.0g / L~30.0g / L, L-malic acid 1.0g / L~3.0g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 2.0g / L~5.0g / L, polyvinyl alcohol 5.0g / L~10.0g / L, the remainder is made up with pure water.

2. The copper etching solution composition for reducing copper corrosion and etching crystallization after stripping and washing as described in claim 1, characterized in that, The mass concentration of the ethylenediaminetetramethylenephosphonic acid is 10 times that of acetone oxime.

3. The copper etching solution composition for reducing copper corrosion and etching crystallization after stripping and washing as described in claim 1, characterized in that, The copper etching solution composition contains the following concentrations of raw materials: Hydrogen peroxide 125g / L, sulfuric acid 55g / L, ethylenediaminetetramethylenephosphonic acid 25g / L, acetone oxime 2.5g / L, glycolic acid 15g / L, phosphoric acid 28.5g / L, L-malic acid 2.0g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 3.0g / L, polyvinyl alcohol 7.8g / L, with the remainder made up with pure water.

4. The copper etching solution composition for reducing copper corrosion and etching crystallization after stripping and washing as described in claim 1, characterized in that, The copper etching solution composition contains the following concentrations of raw materials: Hydrogen peroxide 140g / L, sulfuric acid 50g / L, ethylenediaminetetramethylenephosphonic acid 30g / L, acetone oxime 2.0g / L, glycolic acid 15g / L, phosphoric acid 25g / L, L-malic acid 1.0g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 4.0g / L, polyvinyl alcohol 5.0g / L, with the remainder made up with pure water.

5. The copper etching solution composition for reducing copper corrosion and etching crystallization after stripping and washing as described in claim 1, characterized in that, The copper etching solution composition contains the following concentrations of raw materials: Hydrogen peroxide 130g / L, sulfuric acid 60g / L, ethylenediaminetetramethylenephosphonic acid 20g / L, acetone oxime 3.0g / L, glycolic acid 10.0g / L, phosphoric acid 30.0g / L, L-malic acid 3.0g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 2.0g / L, polyvinyl alcohol 10.0g / L, with the remainder made up with pure water.

6. The copper etching solution composition for reducing copper corrosion and etching crystallization after stripping and washing as described in claim 1, characterized in that, The copper etching solution composition contains the following concentrations of raw materials: Hydrogen peroxide 115.0 g / L, sulfuric acid 52 g / L, ethylenediaminetetramethylenephosphonic acid 25 g / L, acetone oxime 2.8 g / L, glycolic acid 13.5 g / L, phosphoric acid 26.5 g / L, L-malic acid 2.5 g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 4.5 g / L, polyvinyl alcohol 7.2 g / L, with the remainder made up with pure water.

7. The copper etching solution composition for reducing copper corrosion and etching crystallization after stripping and washing as described in claim 1, characterized in that, The copper etching solution composition contains the following concentrations of raw materials: Hydrogen peroxide 110.0 g / L, sulfuric acid 58 g / L, ethylenediaminetetramethylenephosphonic acid 20 g / L, acetone oxime 3.0 g / L, glycolic acid 20.0 g / L, phosphoric acid 30.0 g / L, L-malic acid 1.0 g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 5.0 g / L, polyvinyl alcohol 5.0 g / L, with the remainder made up with pure water.

8. The copper etching solution composition for reducing copper corrosion and etching crystallization after stripping and washing as described in claim 1, characterized in that, The copper etching solution composition contains the following concentrations of raw materials: Hydrogen peroxide 150.0 g / L, sulfuric acid 51 g / L, ethylenediaminetetramethylenephosphonic acid 22 g / L, acetone oxime 2.5 g / L, glycolic acid 10.0 g / L, phosphoric acid 26 g / L, L-malic acid 1.0 g / L, 1,2,3,4,5-pentahydroxyhexanoic acid 3.5 g / L, polyvinyl alcohol 5.0 g / L, with the remainder made up with pure water.

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