CN113604804A - Etching solution for stabilizing line width loss and etching cone angle in panel copper plating process - Google Patents
Etching solution for stabilizing line width loss and etching cone angle in panel copper plating process Download PDFInfo
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Abstract
The invention relates to an etching solution for stabilizing line width loss and etching cone angle in a panel copper plating process. In the invention, hydrogen peroxide, a chelating agent, an etching inhibitor, a wetting agent, a solubilizer, a pH regulator and deionized water form the copper process panel etching solution. In the etching process, with the increase of copper ions in the etching solution, the stability of the etching cone angle and the line width loss can be still maintained. A chelating agent system consisting of the composite organic acid, the pyridine and the derivatives thereof in the etching solution can more quickly form a stable chelate with copper ions generated in etching in a coordination bond mode, so that the influence of the copper ions on the etching rate and the etching life is reduced, and the stability of the etching solution is enhanced; the matching use of the wetting agent and the solubilizer can improve the solubility of the etching solution, enhance the wettability of the etching solution on the surfaces of the photoresist and the copper, and promote copper ions to be quickly dispersed into the etching solution, so that the etching solution can etch a stable cone angle, thereby prolonging the service life of the etching solution and reducing the use cost.
Description
Technical Field
The invention relates to the technical field of electronic chemicals in the thin film transistor industry of liquid crystal displays, in particular to an etching solution for stabilizing line width loss and etching cone angle in a panel copper plating process.
Background
In recent years, flat panel displays have been developed to have large size and high resolution to meet the requirements of end users, but the large size of the panel increases the impedance of the wires and reduces the signal transmission speed. In order to adapt to the development of the panel industry, the metal copper and the metal copper alloy with lower conductivity and excellent electromigration resistance are used for replacing aluminum and the metal copper alloy, so that the impedance and the current loss of a lead can be effectively reduced, the signal transmission speed is improved, and the manufacturing process of a driving IC is simplified.
The etching process is one of the very important processes in the TFT-LCD process, which is mainly a process of removing an object material by etching using some specific physical or chemical reaction. Etching is classified into wet etching and dry etching, wherein the wet etching has been used in the industry for a long time due to advantages of high productivity, high selectivity, and the like. However, the wet etching process also has some disadvantages, the wet etching has an isotropic etching effect, which may cause lateral etching and an etching taper angle, excessive lateral etching may cause a reduction in a wire width of a conductive wire, which may affect electrical characteristics of a product, and an excessive or insufficient etching taper angle may cause defects in a subsequent processing process, which may affect a product yield. Therefore, it is important to develop a copper etching solution that can stably control the line width loss and the etching taper angle.
In order to adapt to the development of the panel industry and meet the process requirements, the invention introduces a chelating agent, an etching inhibitor, a wetting agent, a solubilizer, a pH regulator and the like on the basis of hydrogen peroxide, and regulates, controls and stabilizes the line width loss and the etching cone angle. The invention develops an etching solution for stabilizing line width loss and etching cone angle in a panel copper plating process.
Disclosure of Invention
The invention aims to provide an etching solution for stabilizing line width loss and etching cone angle in a panel copper plating process. The copper etching solution consists of hydrogen peroxide, a chelating agent, an etching inhibitor, a wetting agent, a solubilizer, a pH regulator and deionized water.
Wherein the mass fraction of the hydrogen peroxide is 1-15%; the mass fraction of the chelating agent is 1-10%; the mass fraction of the etching inhibitor is 0.01-0.5%; the mass fraction of the wetting agent is 0.05-1%; the mass fraction of the solubilizer is 0.1-5%; the mass fraction of the pH regulator is 1-5%; the balance being deionized water.
In an embodiment, the chelating agent is composed of a complex organic acid and pyridine and derivatives thereof, wherein the complex organic acid is composed of an organic acid containing carboxyl or hydroxyl and a part of amino acid, wherein the organic acid is mainly one or more of glycolic acid, hydroxypropionic acid, oxalic acid, malonic acid, succinic acid and citric acid, and the amino acid is mainly one or more of glycine, alanine, leucine, methionine, glutamic acid, lysine and arginine; the pyridine and its derivatives are mainly one or more of pyridine, 3-aminopyridine, bipyridine, and 4, 4-diamino-2, 2-bipyridine.
In the embodiment, the etching inhibitor is heterocyclic hydrocarbon containing oxygen or nitrogen, such as one or more of furan, tetrahydrofuran, 2, 5-dimethoxydihydrofuran, 4-aminoimidazole, 2-aminoimidazole, piperazine, acetyl piperazine and 1-acetyl-4-methyl piperazine.
In an embodiment, the wetting agent is one or more of alkyl sodium naphthalene sulfonate, isopropyl sodium naphthalene sulfonate, butyl sodium naphthalene sulfonate and sodium dodecyl benzene sulfonate.
In an embodiment, the solubilizer is one or more of ethylene glycol ethyl ether, diethylene glycol monobutyl ether and propylene glycol ethyl ether.
In an embodiment, the pH adjusting agent may include one or more of ethanolamine, triethanolamine, isopropanolamine, and imidazole.
The invention has the advantages and beneficial effects that: firstly, a chelating agent system consisting of the composite organic acid, the pyridine and the derivatives thereof can more quickly form a stable chelate with copper ions generated in the etching process in a coordination bond mode, so that the influence of the copper ions on the etching rate and the etching life is avoided, and the stability of the etching solution is enhanced; secondly, an etching inhibitor composed of heterocyclic hydrocarbon containing oxygen or nitrogen can effectively control the etching rate and stabilize the line width loss; thirdly, the matching use of the wetting agent and the solubilizer can improve the solubility of the etching solution, enhance the wettability of the etching solution on the photoresist and the copper surface, and simultaneously promote the copper ions on the metal copper surface to be rapidly dispersed into the etching solution, so that the etching solution can etch a stable cone angle under different copper ion concentrations, thereby prolonging the service life of the etching solution and reducing the use cost.
Drawings
Fig. 1 is an SEM image of the copper structural sheet etched by the etching solution in comparative example 1, wherein a is an SEM image of the copper structural sheet after etching when the copper ion concentration is 500ppm, and B is an SEM image of the copper structural sheet after etching when the copper ion concentration is 5000 ppm.
Fig. 2 is an SEM image of the copper structural sheet etched by the etching solution in comparative example 2, wherein a is an SEM image of the copper structural sheet after etching when the copper ion concentration is 500ppm, and B is an SEM image of the copper structural sheet after etching when the copper ion concentration is 6000 ppm.
Fig. 3 is an SEM image of the copper structural sheet etched by the etching solution in comparative example 3, wherein a is an SEM image of the copper structural sheet after etching when the copper ion concentration is 500ppm, and B is an SEM image of the copper structural sheet after etching when the copper ion concentration is 6000 ppm.
Fig. 4 is an SEM image of the etching solution of example 1 after etching the copper structural sheet, wherein a is an SEM image of the etched copper structural sheet when the copper ion concentration is 500ppm, and B is an SEM image of the etched copper structural sheet when the copper ion concentration is 8000 ppm.
FIG. 5 is an SEM image of the copper structure plate etched by the etching solution of example 3, wherein A is the SEM image of the copper structure plate etched with the copper ion concentration of 500ppm, and B is the SEM image of the copper structure plate etched with the copper ion concentration of 8000 ppm.
FIG. 6 is an SEM image of the copper structure plate etched by the etching solution of example 5, wherein A is the SEM image of the copper structure plate etched with the copper ion concentration of 500ppm, and B is the SEM image of the copper structure plate etched with the copper ion concentration of 8000 ppm.
FIG. 7 is an SEM image of a copper structure wafer etched by the etching solution of example 7, wherein A is the SEM image of the copper structure wafer after etching when the concentration of copper ions is 500ppm, and B is the SEM image of the copper structure wafer after etching when the concentration of copper ions is 8000 ppm.
Detailed Description
In order to better understand the present invention, the following will fully describe the examples and comparative examples in connection with the drawings, but the scope of the claimed invention is not limited to the examples shown.
Comparative example 1
Comparative example 1 provides copper etching solution and etching effect of a single chelating agent, specifically:
the copper etching solution consists of hydrogen peroxide, citric acid, isopropanolamine and deionized water.
Wherein the mass fraction of the hydrogen peroxide is 9 percent; the citric acid content is 6%; the mass fraction of isopropanolamine is 3 percent; the balance being deionized water. Firstly, weighing citric acid, dissolving the citric acid by using a proper amount of deionized water, then adding hydrogen peroxide, uniformly mixing, and then adjusting the pH to about 4 by using isopropanolamine.
And heating and stabilizing the copper etching solution at 35 ℃, then placing the cut copper structure piece into the etching solution and slightly shaking until the structure piece is transparent, recording the time required for the copper structure piece to become transparent, namely the etching end point time, and calculating the etching rate. And meanwhile, gradually adding copper powder into the etching solution to 8000ppm, etching the copper structure sheet at different copper ion concentrations, and leaving a sample to shoot an SEM picture to observe indexes such as line width loss, etching cone angle and the like.
In the etching process, the etching rate of the etching solution to copper is faster and faster along with the increase of the concentration of copper ions in the etching solution, the etching rate is 20% higher than the initial etching rate at 5000ppm, and when the concentration of the copper ions is increased again, hydrogen peroxide in the etching solution is decomposed violently, so that the etching solution is heated rapidly and even boils suddenly. The etching results are shown in table 1 and fig. 1.
Comparative example 2
Comparative example 2 provides a copper etching solution without an etching inhibitor and an etching effect, specifically:
the copper etching solution consists of hydrogen peroxide, citric acid, pyridine, isopropanolamine and deionized water.
Wherein the mass fraction of the hydrogen peroxide is 9 percent; the mass fraction of the citric acid is 6 percent; the mass fraction of pyridine is 1 percent; the mass fraction of isopropanolamine is 3 percent; the balance being deionized water. Firstly, weighing citric acid and pyridine, dissolving the citric acid and the pyridine by using a proper amount of deionized water, then adding hydrogen peroxide, uniformly mixing, and then adjusting the pH to about 4 by using isopropanolamine.
The etching step is the same as above. In the etching process, the etching rate of the etching solution to copper is still faster along with the increase of the concentration of copper ions in the etching solution, and when the concentration of the copper ions exceeds 6000ppm, the etching solution does not boil out, but white precipitates appear in the etching solution and the etching rate is greatly reduced. The etching results are shown in table 1 and fig. 2.
Comparative example 3
Comparative example 3 provides a copper etching solution without adding a solubilizer and an etching effect, specifically:
the copper etching solution consists of hydrogen peroxide, citric acid, pyridine, furan, alkyl naphthalene sulfonate, isopropanolamine and deionized water.
Wherein the mass fraction of the hydrogen peroxide is 9 percent; the mass fraction of the citric acid is 6 percent; the mass fraction of pyridine is 1 percent; the mass fraction of furan is 0.05%; 0.1% of sodium alkyl naphthalene sulfonate; the mass fraction of isopropanolamine is 3 percent; the balance being deionized water. Firstly, sequentially weighing citric acid, pyridine and furan, dissolving the citric acid, the pyridine and the furan by using a proper amount of deionized water, then adding sodium alkyl naphthalene sulfonate and hydrogen peroxide, uniformly mixing, and then adjusting the pH to about 4 by using isopropanolamine.
The etching step is the same as above. In the etching process, the etching rate of the etching solution to copper is still faster along with the increase of the concentration of copper ions in the etching solution, and when the concentration of the copper ions exceeds 6000ppm, the etching solution does not boil out, but white precipitates appear in the etching solution and the etching rate is greatly reduced. The etching results are shown in table 1 and fig. 3.
Comparative example 4
Comparative example 4 provides a copper etching solution without adding a wetting agent and an etching effect, specifically:
the copper etching solution consists of hydrogen peroxide, citric acid, pyridine, furan, ethylene glycol ethyl ether, isopropanolamine and deionized water.
Wherein the mass fraction of the hydrogen peroxide is 9 percent; the mass fraction of the citric acid is 6 percent; the mass fraction of pyridine is 1 percent; the mass fraction of furan is 0.05%; the mass fraction of the ethylene glycol monoethyl ether is 2 percent; the mass fraction of isopropanolamine is 3 percent; the balance being deionized water. Firstly, sequentially weighing citric acid, pyridine and furan, dissolving the citric acid, the pyridine and the furan by using a proper amount of deionized water, then adding ethylene glycol ethyl ether and hydrogen peroxide, uniformly mixing, and then adjusting the pH to about 4 by using isopropanolamine.
The etching step is the same as above. In the whole etching process, the etching rate of the etching solution to copper cannot be changed due to the change of the concentration of copper ions, no precipitate is generated in the etching solution, and when the concentration of the copper ions exceeds 8000ppm, the etching rate of the etching solution is gradually reduced, but the etching cone angle and the line width loss of the etching solution are greatly changed. The etching effect of etching taper angle and line width loss was similar to that of fig. 3, and the etching results are shown in table 1.
Example 1
Embodiment 1 provides an etching solution for stabilizing line width loss and etching taper angle in a panel copper plating process, which specifically comprises:
the copper etching solution consists of hydrogen peroxide, citric acid, glycolic acid, alanine, bipyridyl, furan, sodium alkyl naphthalene sulfonate, ethylene glycol ethyl ether, imidazole and deionized water.
Wherein the mass fraction of the hydrogen peroxide is 9 percent; the mass fraction of the citric acid is 6 percent; the mass fraction of glycolic acid is 1 percent; the mass fraction of alanine is 1%; the mass fraction of bipyridine is 1.5%; the mass fraction of furan is 0.05%; 0.1% of sodium alkyl naphthalene sulfonate; the mass fraction of the ethylene glycol monoethyl ether is 2 percent; the mass fraction of imidazole is 2%; the balance being deionized water. Firstly, sequentially weighing citric acid, glycollic acid, alanine, bipyridine, furan and alkyl naphthalene sodium sulfonate, dissolving the citric acid, glycollic acid, alanine, bipyridine, furan and alkyl naphthalene sodium sulfonate by using a proper amount of deionized water, then adding ethylene glycol ethyl ether, imidazole and hydrogen peroxide, uniformly mixing, and then adjusting the pH to about 4 by using imidazole.
The etching step is the same as above. In the whole etching process, the etching rate of the etching solution to copper cannot be changed due to the change of the concentration of copper ions, no precipitate is generated in the etching solution, and when the concentration of the copper ions exceeds 8000ppm, the etching rate of the etching solution is gradually reduced. The etching results are shown in table 1 and fig. 4.
Example 2
Embodiment 2 provides an etching solution for stabilizing line width loss and etching taper angle in a panel copper plating process, which specifically comprises:
the copper etching solution consists of hydrogen peroxide, malic acid, oxalic acid, glutamic acid, 4-diamino-2, 2-bipyridine, furan, sodium alkyl naphthalene sulfonate, ethylene glycol ethyl ether, imidazole and deionized water.
Wherein the mass fraction of the hydrogen peroxide is 9 percent; the mass fraction of malic acid is 6%; the mass fraction of oxalic acid is 1 percent; the mass fraction of glutamic acid is 1%; the mass fraction of the 4, 4-diamino-2, 2-bipyridyl is 1.5 percent; the mass fraction of furan is 0.05%; 0.1% of sodium alkyl naphthalene sulfonate; the mass fraction of the ethylene glycol monoethyl ether is 2 percent; the mass fraction of imidazole is 2%; the balance being deionized water. Firstly, sequentially weighing malic acid, oxalic acid, glutamic acid, 4-diamino-2, 2-bipyridine, furan and alkyl naphthalene sodium sulfonate, dissolving the malic acid, the oxalic acid, the glutamic acid, the 4, 4-diamino-2, 2-bipyridine, the furan and the alkyl naphthalene sodium sulfonate by using a proper amount of deionized water, then adding ethylene glycol ethyl ether, imidazole and hydrogen peroxide, uniformly mixing, and then adjusting the pH to about 4 by using imidazole.
The etching step is the same as above. In the whole etching process, the etching rate of the etching solution to copper cannot be changed due to the change of the concentration of copper ions, no precipitate is generated in the etching solution, and when the concentration of the copper ions exceeds 8000ppm, the etching rate of the etching solution is gradually reduced. The etching effect was similar to that of fig. 4, and the etching results are shown in table 1.
Example 3
Embodiment 3 provides an etching solution for stabilizing line width loss and etching taper angle in a panel copper plating process, which specifically comprises:
the copper etching solution consists of hydrogen peroxide, citric acid, glycolic acid, lysine, 3-aminopyridine, piperazine, alkyl naphthalene sulfonic acid sodium, ethylene glycol ethyl ether, imidazole and deionized water.
Wherein the mass fraction of the hydrogen peroxide is 9 percent; the mass fraction of the citric acid is 6 percent; the mass fraction of glycolic acid is 1 percent; the mass fraction of lysine is 1 percent; the mass fraction of the 3-aminopyridine is 1.5 percent; the mass fraction of piperazine is 0.05%; 0.1% of sodium alkyl naphthalene sulfonate; the mass fraction of the ethylene glycol monoethyl ether is 2 percent; the mass fraction of imidazole is 2%; the balance being deionized water. Firstly, sequentially weighing citric acid, glycollic acid, lysine, 3-aminopyridine, piperazine and alkyl sodium naphthalene sulfonate, dissolving the materials by using a proper amount of deionized water, then adding ethylene glycol ethyl ether, imidazole and hydrogen peroxide, uniformly mixing, and adjusting the pH value to about 4 by using imidazole.
The etching step is the same as above. In the whole etching process, the etching rate of the etching solution to copper cannot be changed due to the change of the concentration of copper ions, no precipitate is generated in the etching solution, and when the concentration of the copper ions exceeds 8000ppm, the etching rate of the etching solution is gradually reduced. The etching results are shown in table 1 and fig. 5.
Example 4
Embodiment 4 provides an etching solution for stabilizing line width loss and etching taper angle in a panel copper plating process, which specifically comprises:
the copper etching solution consists of hydrogen peroxide, citric acid, glycolic acid, lysine, bipyridyl, acetyl piperazine, sodium alkyl naphthalene sulfonate, ethylene glycol ethyl ether, imidazole and deionized water.
Wherein the mass fraction of the hydrogen peroxide is 9 percent; the mass fraction of the citric acid is 6 percent; the mass fraction of glycolic acid is 1 percent; the mass fraction of lysine is 1 percent; the mass fraction of bipyridine is 1.5%; the mass fraction of the acetylpiperazine is 0.05 percent; 0.1% of sodium alkyl naphthalene sulfonate; the mass fraction of the ethylene glycol monoethyl ether is 2 percent; the mass fraction of imidazole is 2%; the balance being deionized water. Firstly, sequentially weighing citric acid, glycollic acid, lysine, bipyridine, acetyl piperazine and sodium alkyl naphthalene sulfonate, dissolving the citric acid, the glycollic acid, the lysine, the bipyridine, the acetyl piperazine and the sodium alkyl naphthalene sulfonate by using a proper amount of deionized water, then adding ethylene glycol ethyl ether, imidazole and hydrogen peroxide, uniformly mixing, and then adjusting the pH value to about 4 by using the imidazole.
The etching step is the same as above. In the whole etching process, the etching rate of the etching solution to copper cannot be changed due to the change of the concentration of copper ions, no precipitate is generated in the etching solution, and when the concentration of the copper ions exceeds 8000ppm, the etching rate of the etching solution is gradually reduced. The etching effect was similar to that of fig. 5, and the etching results are shown in table 1.
Example 5
the copper etching solution consists of hydrogen peroxide, citric acid, succinic acid, glycine, bipyridine, 1-acetyl-4-methylpiperazine, butyl naphthalene sodium sulfonate, ethylene glycol ethyl ether, imidazole and deionized water.
Wherein the mass fraction of the hydrogen peroxide is 9 percent; the mass fraction of the citric acid is 6 percent; the mass fraction of the succinic acid is 1 percent; the mass fraction of glycine is 1%; the mass fraction of bipyridine is 1.5%; the mass fraction of the 1-acetyl-4-methylpiperazine is 0.05%; 0.1 percent of butyl sodium naphthalene sulfonate; the mass fraction of the ethylene glycol butyl ether is 2 percent; the mass fraction of imidazole is 2%; the balance being deionized water. Firstly, sequentially weighing citric acid, succinic acid, glycine, bipyridine, 1-acetyl-4-methylpiperazine and butyl naphthalene sodium sulfonate, dissolving the citric acid, the succinic acid, the glycine, the bipyridine, the 1-acetyl-4-methylpiperazine and the butyl naphthalene sodium sulfonate by using a proper amount of deionized water, then adding ethylene glycol ethyl ether, imidazole and hydrogen peroxide, uniformly mixing, and then adjusting the pH value to about 4 by using the imidazole.
The etching step is the same as above. In the whole etching process, the etching rate of the etching solution to copper cannot be changed due to the change of the concentration of copper ions, no precipitate is generated in the etching solution, and when the concentration of the copper ions exceeds 8000ppm, the etching rate of the etching solution is gradually reduced. The etching results are shown in table 1 and fig. 6.
Example 6
Embodiment 6 provides an etching solution for stabilizing line width loss and etching taper angle in a panel copper plating process, which specifically comprises:
the copper etching solution is composed of hydrogen peroxide, citric acid, succinic acid, arginine, bipyridine, acetyl piperazine, sodium dodecyl benzene sulfonate, ethylene glycol ethyl ether, imidazole and deionized water.
Wherein the mass fraction of the hydrogen peroxide is 9 percent; the mass fraction of the citric acid is 6 percent; the mass fraction of the succinic acid is 1 percent; 1% of arginine by mass; the mass fraction of bipyridine is 1.5%; the mass fraction of the acetylpiperazine is 0.05 percent; sodium dodecyl benzene sulfonate of 0.1%; the mass fraction of the ethylene glycol monoethyl ether is 2 percent; the mass fraction of imidazole is 2%; the balance being deionized water. Firstly, sequentially weighing citric acid, succinic acid, arginine, bipyridine, acetyl piperazine and sodium dodecyl benzene sulfonate, dissolving the citric acid, the succinic acid, the arginine, the bipyridine, the acetyl piperazine and the sodium dodecyl benzene sulfonate by using a proper amount of deionized water, then adding ethylene glycol ethyl ether, imidazole and hydrogen peroxide, uniformly mixing, and then adjusting the pH value to about 4 by using the imidazole.
The etching step is the same as above. In the whole etching process, the etching rate of the etching solution to copper cannot be changed due to the change of the concentration of copper ions, no precipitate is generated in the etching solution, and when the concentration of the copper ions exceeds 8000ppm, the etching rate of the etching solution is gradually reduced. The etching effect was similar to that of fig. 6, and the etching results are shown in table 1.
Example 7
Embodiment 7 provides an etching solution for stabilizing line width loss and etching taper angle in a panel copper plating process, which specifically comprises:
the copper etching solution consists of hydrogen peroxide, citric acid, succinic acid, methionine, bipyridine, 4-aminoimidazole, sodium dodecyl benzene sulfonate, diethylene glycol monobutyl ether, imidazole and deionized water.
Wherein the mass fraction of the hydrogen peroxide is 9 percent; the mass fraction of the citric acid is 6 percent; the mass fraction of the succinic acid is 1 percent; the mass fraction of methionine is 1%; the mass fraction of bipyridine is 1.5%; the mass fraction of the 4-aminoimidazole is 0.05 percent; sodium dodecyl benzene sulfonate of 0.1%; the mass fraction of the diethylene glycol monobutyl ether is 2 percent; the mass fraction of imidazole is 2%; the balance being deionized water. Firstly, sequentially weighing citric acid, succinic acid, methionine, bipyridine, 4-aminoimidazole and sodium dodecyl benzene sulfonate, dissolving the materials by using a proper amount of deionized water, then adding diethylene glycol monobutyl ether, imidazole and hydrogen peroxide, uniformly mixing, and then adjusting the pH value to about 4 by using imidazole.
The etching step is the same as above. In the whole etching process, the etching rate of the etching solution to copper cannot be changed due to the change of the concentration of copper ions, no precipitate is generated in the etching solution, and when the concentration of the copper ions exceeds 8000ppm, the etching rate of the etching solution is gradually reduced. The etching results are shown in table 1 and fig. 7.
Example 8
the copper etching solution consists of hydrogen peroxide, citric acid, succinic acid, leucine, bipyridine, 2, 5-dimethoxy dihydrofuran, sodium dodecyl benzene sulfonate, diethylene glycol monobutyl ether, isopropanolamine and deionized water.
Wherein the mass fraction of the hydrogen peroxide is 9 percent; the mass fraction of the citric acid is 6 percent; the mass fraction of the succinic acid is 1 percent; the mass fraction of leucine is 1 percent; the mass fraction of bipyridine is 1.5%; the mass fraction of the 2, 5-dimethoxydihydrofuran is 0.05 percent; sodium dodecyl benzene sulfonate of 0.1%; the mass fraction of the diethylene glycol monobutyl ether is 2 percent; the mass fraction of isopropanolamine is 4%; the balance being deionized water. Firstly, sequentially weighing citric acid, succinic acid, leucine, bipyridine, 2, 5-dimethoxy dihydrofuran and sodium dodecyl benzene sulfonate, dissolving the materials by using a proper amount of deionized water, then adding diethylene glycol monobutyl ether, isopropanolamine and hydrogen peroxide, uniformly mixing, and then adjusting the pH value to about 4 by using isopropanolamine.
The etching step is the same as above. In the whole etching process, the etching rate of the etching solution to copper cannot be changed due to the change of the concentration of copper ions, no precipitate is generated in the etching solution, and when the concentration of the copper ions exceeds 8000ppm, the etching rate of the etching solution is gradually reduced. The etching effect was similar to that of fig. 6, and the etching results are shown in table 1.
Example 9
The procedure and procedure were as in example 1 except that citric acid, glycolic acid, alanine and bipyridine were used in amounts of 8%, 1.5% and 2.0%, respectively. The etching results are shown in Table 1.
Example 10
The procedure and procedure were as in example 1, except that the chelating agent was glycolic acid, which was used in an amount of 0.5%.
In the etching process, less chelating agents cannot timely chelate divalent copper ions, and free copper ions can catalyze hydrogen peroxide to decompose to accelerate hydrogen peroxide decomposition, so that the etching solution is rapidly heated and even boils. The etching results are shown in Table 1.
Example 11
The method and the steps are the same as the example 1, only the chelating agent is citric acid and alanine, wherein the dosage of the citric acid and the dosage of the alanine are respectively 0.3 percent and 0.5 percent.
In the etching process, less chelating agents cannot timely chelate divalent copper ions, and free copper ions can catalyze hydrogen peroxide to decompose to accelerate hydrogen peroxide decomposition, so that the etching solution is rapidly heated and even boils. The etching results are shown in Table 1.
Example 12
The method and the steps are the same as example 1, only the chelating agent is bipyridine, and the dosage of the bipyridine is 3.8%.
In the process of preparing the etching solution, excessive bipyridyl is difficult to dissolve, and even solid bipyridyl floats on the surface of the etching solution. The etching results are shown in Table 1.
Example 13
The method and procedure were the same as example 3, except that the etching inhibitor was 0.65%, and the etching results are shown in Table 1.
Example 14
The method and procedure were the same as example 3, except that the etching inhibitor was 0.001%, and the etching results are shown in Table 1.
Example 15
The procedure and procedure were as in example 7, except that the solubilizer was ethylene glycol.
During the etching process, a small amount of white or blue precipitate appears in the etching solution. The etching results are shown in Table 1.
Example 16
The procedure and procedure were as in example 7, except that the solubilizer was acetone.
During the etching process, a small amount of white or blue precipitate appears in the etching solution. The etching results are shown in Table 1.
Example 17
The procedure and procedure were as in example 7, except that the amount of the solubilizer diethylene glycol monobutyl ether added was 0.08%.
During the etching process, a small amount of white or blue precipitate appears in the etching solution. The etching results are shown in Table 1.
Example 18
The process and procedure were the same as in example 7 except that the amount of the solubilizer diethylene glycol monobutyl ether added was 5.8%, and the etching results are shown in Table 1.
TABLE 1
Claims (6)
1. An etching solution for stabilizing line width loss and etching cone angle in a panel copper process is characterized in that: hydrogen peroxide, a chelating agent, an etching inhibitor, a wetting agent, a solubilizer, a pH regulator and deionized water, wherein the mass fraction of the hydrogen peroxide in the copper etching liquid is 1-15%; the mass fraction of the chelating agent is 1-10%; the mass fraction of the etching inhibitor is 0.01-0.5%; the mass fraction of the wetting agent is 0.05-1%; the mass fraction of the solubilizer is 0.1-5%; the mass fraction of the pH regulator is 1-5%; the balance being deionized water.
2. The etching solution for stabilizing line width loss and etching cone angle in a panel copper plating process according to claim 1, wherein: the chelating agent consists of composite organic acid, pyridine and derivatives thereof, wherein the composite organic acid consists of organic acid containing carboxyl or hydroxyl and partial amino acid, and the organic acid is one or more of glycolic acid, hydroxypropionic acid, oxalic acid, malonic acid, succinic acid and citric acid; the amino acid is one or more of glycine, alanine, leucine, methionine, glutamic acid, lysine and arginine; the pyridine and its derivatives are one or more of pyridine, 3-aminopyridine, bipyridine, and 4, 4-diamino-2, 2-bipyridine.
3. The etching solution for stabilizing line width loss and etching cone angle in a panel copper plating process according to claim 1, wherein: the etching inhibitor is heterocyclic hydrocarbon containing oxygen or nitrogen, and is one or more of furan, tetrahydrofuran, 2, 5-dimethoxy dihydrofuran, 4-aminoimidazole, 2-aminoimidazole, piperazine, acetyl piperazine and 1-acetyl-4-methyl piperazine.
4. The etching solution for stabilizing line width loss and etching cone angle in a panel copper plating process according to claim 1, wherein: the wetting agent is one or more of alkyl naphthalene sodium sulfonate, isopropyl naphthalene sodium sulfonate, butyl naphthalene sodium sulfonate and sodium dodecyl benzene sulfonate.
5. The etching solution for stabilizing line width loss and etching cone angle in a panel copper plating process according to claim 1, wherein: the solubilizer is one or more of ethylene glycol ethyl ether, diethylene glycol monobutyl ether and propylene glycol ethyl ether.
6. The etching solution for stabilizing line width loss and etching cone angle in a panel copper plating process according to claim 1, wherein: the pH regulator is one or more of ethanolamine, triethanolamine, isopropanolamine and imidazole.
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