阅读说明：本技术 铜铝膜蚀刻液 (Etching solution for copper aluminum film ) 是由 吴豪旭 于 2021-01-11 设计创作，主要内容包括：本申请实施例公开了一种铜铝膜蚀刻液,所述铜铝膜蚀刻液相对于所述蚀刻液的总重量,以重量计,包含：4％至10％的过氧化氢,0.1％至1％的过氧化氢稳定剂,0.05％至0.5％的蚀刻抑制剂,10％至30％的螯合剂,0.2％至2％的表面活性剂,0.2％至5％的无机磷酸盐或无机磷酸氢盐,0.1％至5％的无机酸,0至0.05％的氟化物以及余量的去离子水。本申请蚀刻液具有较长的使用寿命。(The embodiment of the application discloses copper aluminium membrane etching solution, copper aluminium membrane etching solution for the total weight of etching solution contains by weight: 4 to 10% hydrogen peroxide, 0.1 to 1% hydrogen peroxide stabilizer, 0.05 to 0.5% etching inhibitor, 10 to 30% chelating agent, 0.2 to 2% surfactant, 0.2 to 5% inorganic phosphate or inorganic hydrogen phosphate, 0.1 to 5% inorganic acid, 0 to 0.05% fluoride and the balance deionized water. The etching solution has a long service life.)

1. A copper-aluminum film etching solution, characterized by comprising, by weight relative to the total weight of the etching solution: 4 to 10% hydrogen peroxide, 0.1 to 1% hydrogen peroxide stabilizer, 0.05 to 0.5% etching inhibitor, 10 to 30% chelating agent, 0.2 to 2% surfactant, 0.2 to 5% inorganic phosphate or inorganic hydrogen phosphate, 0.1 to 5% inorganic acid, 0 to 0.05% fluoride and the balance deionized water.

2. The copper-aluminum film etching solution according to claim 1, characterized by comprising 0.005% to 0.05% by weight of fluoride with respect to the total weight of the etching solution.

3. The copper-aluminum film etching solution as claimed in claim 1, wherein the hydrogen peroxide stabilizer is selected from phenylurea, N' -diphenylurea or diphenylsemicarbazide.

4. The copper-aluminum film etching solution as recited in claim 1, wherein the etching inhibitor is selected from benzoxazole compounds.

5. The copper-aluminum film etching solution as recited in claim 1, wherein the chelating agent is composed of an organic acid and an alcohol amine; the organic acid is 8 to 20% by weight relative to the total weight of the etching solution, and the alcohol amine is 2 to 10% by weight relative to the total weight of the etching solution.

6. The copper-aluminum film etching solution according to claim 5, wherein the organic acid is at least one selected from the group consisting of citric acid, malonic acid, diglycolic acid, maleic acid, hydroxybutyric acid, succinic acid, malic acid, glycolic acid, phthalic acid, salicylic acid, alanine, asparagine and arginine; the alcohol amine is at least one selected from N, N-dimethylethanolamine, N-diethylethanolamine, 2-amino-2-methyl-1-propanol, isopropanolamine, diethanolamine, triisopropanolamine and monoethanolamine.

7. The copper-aluminum film etching solution as recited in claim 1, wherein the surfactant is polyethylene glycol.

8. The etching solution for copper-aluminum film according to claim 1, wherein the inorganic phosphate or inorganic hydrogen phosphate is selected from ammonium salt, potassium salt or sodium salt.

9. The copper-aluminum film etching solution according to claim 1, wherein the inorganic acid is at least one selected from phosphoric acid, sulfuric acid, and nitric acid.

10. The copper-aluminum film etching solution according to claim 1, wherein the fluoride is at least one selected from hydrofluoric acid, ammonium fluoride, potassium fluoride, and sodium fluoride.

Technical Field

The application relates to the technical field of etching solutions, in particular to a copper-aluminum film etching solution.

Background

At present, amorphous silicon Thin film transistor products are commonly used in the production process of a Thin film transistor liquid crystal display (TFT-LCD) of advanced generation, and copper, aluminum and alloys thereof are developed and applied due to lower cost. The copper/aluminum film layer becomes the main Gate (Gate) and Source/Drain (Source/Drain) metal layer structure of the TFT-LCD, and the development of the related etching solution is also very important.

Most of the existing etching solutions for copper and aluminum films adopt a hydrogen peroxide system, copper and aluminum are oxidized by hydrogen peroxide, and then copper ions and aluminum ions are generated under the action of acid to finally achieve the purpose of etching, but the copper ions have a catalytic effect on the decomposition of the hydrogen peroxide, when the concentration of the copper ions dissolved in the etching solution exceeds 0.005 g/ml (5000ppm, ppm is parts per million) in the etching process, the hydrogen peroxide can be violently decomposed to cause easy boiling and explosion and reduce the etching efficiency, the etching solution can reach the service life too early, and the etching solution needs to be frequently replaced by new etching solution.

Disclosure of Invention

The embodiment of the application provides a copper aluminium membrane etching solution, can make the etching solution have longer life, and hydrogen peroxide content is low simultaneously, has reduced the cost of etching solution, has improved the security of etching solution.

The embodiment of the application provides a copper aluminum film etching solution, for the total weight of the etching solution, by weight, contains: 4 to 10% hydrogen peroxide, 0.1 to 1% hydrogen peroxide stabilizer, 0.05 to 0.5% etching inhibitor, 10 to 30% chelating agent, 0.2 to 2% surfactant, 0.2 to 5% inorganic phosphate or inorganic hydrogen phosphate, 0.1 to 5% inorganic acid, 0 to 0.05% fluoride and the balance deionized water.

Optionally, in some embodiments of the present application, the fluoride is included in an amount of 0.005% to 0.05% by weight, relative to the total weight of the etching solution.

Alternatively, in some embodiments herein, the hydrogen peroxide stabilizer is selected from phenyl urea, N' -diphenyl urea, or diphenyl semicarbazide.

Optionally, in some embodiments herein, the etch inhibitor is selected from benzoxazole compounds.

Optionally, in some embodiments herein, the chelating agent consists of an organic acid and an alcohol amine; the organic acid is 8 to 20% by weight relative to the total weight of the etching solution, and the alcohol amine is 2 to 10% by weight relative to the total weight of the etching solution.

Optionally, in some embodiments herein, the organic acid is selected from at least one of citric acid, malonic acid, diglycolic acid, maleic acid, hydroxybutyric acid, succinic acid, malic acid, glycolic acid, phthalic acid, salicylic acid, alanine, asparagine, and arginine; the alcohol amine is at least one selected from N, N-dimethylethanolamine, N-diethylethanolamine, 2-amino-2-methyl-1-propanol, isopropanolamine, diethanolamine, triisopropanolamine and monoethanolamine.

Alternatively, in some embodiments of the present application, the organic acid is 8% to 20% by weight relative to the total weight of the etching solution, and the alcohol amine is 2% to 10% by weight relative to the total weight of the etching solution.

Optionally, in some embodiments of the present application, the surfactant is polyethylene glycol.

Optionally, in some embodiments herein, the inorganic phosphate or inorganic hydrogen phosphate salt is selected from an ammonium salt, a potassium salt, or a sodium salt.

Optionally, in some embodiments herein, the inorganic acid is selected from at least one of phosphoric acid, sulfuric acid, and nitric acid.

Optionally, in some embodiments of the present application, the fluoride is selected from at least one of hydrofluoric acid, ammonium fluoride, potassium fluoride, and sodium fluoride.

The etching solution provided by the embodiment of the application can be directly used until the concentration of copper ions is 0.012 g/ml (12000ppm) without adding additives or sub-solutions to supplement components in the etching process, has a long service life, is stable in the etching process, is moderate in etching rate, is stable in an etching angle between 35 and 75 degrees, has no metal residue and no undercut, has low hydrogen peroxide content in the etching solution provided by the embodiment of the application, can avoid an bumping phenomenon caused by overhigh hydrogen peroxide content, improves the safety of the etching solution, is convenient for industrial processing, and reduces the cost of the etching solution.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

FIG. 1 is a scanning electron microscope image of an LCD-TFT glass substrate having a copper-aluminum laminated structure etched by an etching solution provided in an embodiment of the present application;

FIG. 2 is a scanning electron microscope image of an LCD-TFT glass substrate having a copper-aluminum laminated structure etched by the etching solution provided in the first embodiment of the present application;

FIG. 3 is a scanning electron microscope image of the etching solution provided in the embodiment of the present application etching an LCD-TFT glass substrate having a copper-molybdenum stacked structure for 60 seconds.

Detailed Description

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, 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 application.

The embodiment of the application provides a copper-aluminum film etching solution. The following are detailed below. It should be noted that the following description of the embodiments is not intended to limit the preferred order of the embodiments. In addition, in the description of the present application, the term "including" means "including but not limited to". Various embodiments of the invention may exist in a range of versions; it is to be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention; accordingly, the described range descriptions should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, it is contemplated that the description of a range from 1 to 6 has specifically disclosed sub-ranges such as, for example, from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within a range such as, for example, 1, 2, 3, 4, 5, and 6, as applicable regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any number (fractional or integer) recited within the indicated range.

The embodiment of the application provides a copper aluminium membrane etching solution, the definition of copper aluminium membrane includes: a stacked film layer formed by the copper film and the aluminum film (the stacking sequence is not limited); or a single alloy material film layer formed by copper-aluminum alloy.

The etching solution for copper and aluminum films comprises the following components in weight (wt) relative to the total weight of the etching solution: 4 to 10% hydrogen peroxide, 0.1 to 1% hydrogen peroxide stabilizer, 0.05 to 0.5% etching inhibitor, 10 to 30% chelating agent, 0.2 to 2% surfactant, 0.2 to 5% inorganic phosphate or inorganic hydrogen phosphate, 0.1 to 5% inorganic acid, 0 to 0.05% fluoride and the balance deionized water.

It is understood that the mass percentage of the hydrogen peroxide in the etching solution may be any value between 4% and 10%, and may take an integer value, for example: 4%, 5%, 6%, 7%, 8%, 9% or 10%, and may also take on non-integer values, such as: 4.3%, 4.5%, 4.8%, 5.3%, 5.5%, 5.8%, 6.3%, 6.5%, 6.8%, 7.3%, 7.5%, 7.8%, 8.3%, 8.5%, 8.8%, 9.3%, 9.5%, 9.8% or other non-integer values not listed between 4% and 10%, preferably between 4% and 7%.

It can be understood that the mass percentage of the hydrogen peroxide stabilizer in the etching solution can be any value between 0.1% and 1%, for example: 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1% or other non-listed values between 0.1% and 1%, preferably 0.3% to 0.5%.

It can be understood that the mass percentage of the etching inhibitor in the etching solution can be any value between 0.05% and 0.5%, for example: 0.05%, 0.07%, 0.09%, 0.1%, 0.12%, 0.15%, 0.17%, 0.19%, 0.2%, 0.22%, 0.24%, 0.26%, 0.28%, 0.3%, 0.32%, 0.34%, 0.36%, 0.38%, 0.4%, 0.42%, 0.44%, 0.46%, 0.48%, 0.5% or other non-listed values between 0.05% and 0.5%, preferably 0.1% to 0.3%.

It is understood that the mass percentage of the chelating agent in the etching solution may be any value between 10% and 30%, and may take an integer value, for example: 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30%, and may take non-integer values, such as: 10.3%, 10.5%, 10.8%, 11.3%, 11.5%, 11.8%, 12.3%, 12.5%, 12.8%, 13.3%, 13.5%, 13.8%, 14.3%, 14.5%, 14.8%, 15.3%, 15.5%, 15.8%, 16.3%, 16.5%, 16.8%, 17.3%, 17.5%, 17.8%, 18.3%, 18.5%, 18.8%, 19.3%, 19.5%, 19.8%, 20.3%, 20.5%, 20.8%, 21.3%, 21.5%, 21.8%, 22.3%, 22.5%, 22.8%, 23.3%, 23.5%, 23.8%, 24.3%, 24.5%, 24.8%, 25.3%, 25.5%, 25.8%, 26.3%, 26.5%, 26.8%, 27.3%, 27.5%, 27.8%, 28.3%, 28.5%, 28.8%, 29.5%, 29.8%, 29.5%, 29.8% or more preferably between the other integer values of the percentage is between 30% and 29.5%.

It is understood that the mass percentage of the surfactant in the etching solution can be any value between 0.2% and 2%, for example: 0.2%, 0.23%, 0.25%, 0.28%, 0.3%, 0.33%, 0.35%, 0.38%, 0.4%, 0.43%, 0.45%, 0.48%, 0.5%, 0.53%, 0.55%, 0.58%, 0.6%, 0.63%, 0.65%, 0.68%, 0.7%, 0.73%, 0.75%, 0.78%, 0.8%, 0.83%, 0.85%, 0.88%, 0.9%, 0.93%, 0.95%, 0.98%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, or other non-listed values between 0.2% and 2%, preferably 0.3% and 0.8%.

It is understood that the mass percentage of the inorganic phosphate or inorganic hydrogen phosphate in the etching solution can be any value between 0.2% and 5%, for example: 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.3%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.3%, 4.5%, 4.8%, 5% or other non-listed values between 0.2% and 5%, preferably 1% to 3%.

It is understood that the mass percentage of the inorganic acid in the etching solution can be any value between 0.1% and 5%, for example: 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.3%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.3%, 4.5%, 4.8%, 5% or other non-listed values between 0.1% and 5%, preferably 1% to 2%.

It is understood that the mass percentage of the fluoride in the etching solution can be any value between 0 and 0.05%, for example: 0. 0.001%, 0.003%%, 0.005%, 0.007%, 0.009%, 0.01%, 0.013%, 0.015%, 0.018%, 0.02%, 0.023%, 0.025%, 0.028%, 0.03%, 0.033%, 0.035%, 0.038%, 0.04%, 0.043%, 0.045%, 0.048%, 0.05% or other unrecited values between 0 and 0.05%. When the mass percentage of the fluoride in the etching solution is 0, the etching solution does not contain the fluoride; when the etching solution contains the fluoride, the mass percentage of the fluoride in the etching solution is preferably in the range of 0.005% to 0.05%. The etching solution of the embodiment of the present application may contain the fluoride, and the etching rate of the etching solution may be increased by adding the fluoride into the etching solution, but the etching solution may have the problem of insecurity and environmental pollution due to the fluoride, and the etching solution of the embodiment of the present application may also not contain the fluoride, so that the etching solution without fluorine is safer and more environmental friendly, and the etching efficiency may be reduced after the fluoride is removed from the etching solution, and the etching solution of the embodiment of the present application may have almost no difference in the etching effect before and after the fluoride is added to the etching solution by matching of the components and the proportions.

Alternatively, in some embodiments herein, the hydrogen peroxide stabilizer is selected from phenyl urea, N' -diphenyl urea, or diphenyl semicarbazide. The hydrogen peroxide stabilizer can prevent hydrogen peroxide from being severely decomposed, so that the hydrogen peroxide can smoothly and fully play a role.

Optionally, in some embodiments herein, the etch inhibitor is selected from benzoxazole compounds. The benzoxazole compound may be benzotriazole or 5-amino-1H-tetrazole monohydrate. The etch inhibitor is used to control the etch rate and etch angle.

Optionally, in some embodiments herein, the chelating agent consists of an organic acid and an alcohol amine.

Optionally, in some embodiments herein, the organic acid is selected from at least one of citric acid, malonic acid, diglycolic acid, maleic acid, hydroxybutyric acid, succinic acid, malic acid, glycolic acid, phthalic acid, salicylic acid, alanine, asparagine, and arginine; the alcohol amine is at least one selected from N, N-dimethylethanolamine, N-diethylethanolamine, 2-amino-2-methyl-1-propanol, isopropanolamine, diethanolamine, triisopropanolamine and monoethanolamine. The chelating agent can effectively regulate and control the etching rate of the etching solution, is beneficial to etching copper and aluminum, is beneficial to removing metal residues, and further obtains a good wiring section shape.

Alternatively, in some embodiments of the present application, the organic acid is 8% to 20% by weight relative to the total weight of the etching solution, and the alcohol amine is 2% to 10% by weight relative to the total weight of the etching solution. It can be understood that the mass percentage of the organic acid in the etching solution can be any value between 8% and 20%, for example: 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20 or other non-listed values between 8% and 20%, preferably 8% to 10%; the mass percentage of the alcohol amine in the etching solution can be any value between 2% and 10%, for example: 2%, 2.3%, 2.5%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.3%, 4.5%, 4.8%, 5%, 5.3%, 5.5%, 5.8%, 6%, 6.3%, 6.5%, 6.8%, 7%, 7.3%, 7.5%, 7.8%, 8%, 8.3%, 8.5%, 8.8%, 9%, 9.3%, 9.5%, 9.8%, 10% or other non-listed values between 2% and 10%, preferably between 5% and 8%. This application embodiment adopts organic acid and alkylol amine jointly to act as the chelating agent can slow down the decomposition of hydrogen peroxide to the life of extension etching solution, organic acid and alkylol amine can be attached to the metal surface simultaneously, prevent that the metal from being overetched, and then guarantee the etching angle.

Optionally, in some embodiments herein, the surfactant is a polyethylene glycol, such as polyethylene glycol 400 or polyethylene glycol 200. The surfactant is beneficial to etching of the etching solution, so that the surface of the copper-aluminum film and fine gaps can be well contacted in the etching process, a good etching inclination angle is achieved after etching, and no metal residue exists.

Optionally, in some embodiments herein, the inorganic phosphate or inorganic hydrogen phosphate salt is selected from an ammonium salt, a potassium salt, or a sodium salt. The inorganic phosphate or the hydrogen phosphate can stabilize the pH of the system, control the pH range of the etching solution between 2 and 5, prevent overlarge acidity caused by too low pH, damage other film layers in the etching process, prevent hydrogen peroxide from decomposing caused by too high pH to be unfavorable for the smooth proceeding of the etching reaction, and is favorable for prolonging the service life of the etching solution.

Optionally, in some embodiments herein, the inorganic acid is selected from at least one of phosphoric acid, sulfuric acid, and nitric acid.

Optionally, in some embodiments of the present application, the fluoride is selected from at least one of hydrofluoric acid, ammonium fluoride, potassium fluoride, and sodium fluoride. The fluoride has fluorine ions, and the activity of the fluorine ions is strong, so that the etching rate can be accelerated.

The embodiment of the application also provides a preparation method of the etching solution for the copper aluminum film, which comprises the following steps: dissolving the components of the etching solution in deionized water, and stirring and dissolving for 1.5 to 3 hours (h) at the temperature of 15 to 30 ℃ and at the speed of 150 to 800 revolutions per minute until a clear, transparent and uniform mixed solution is presented.

The first embodiment,

The embodiment provides a copper-aluminum film etching solution, which comprises the following components in percentage by weight relative to the total weight of the etching solution: 6.3% hydrogen peroxide, 0.5% phenylurea (hydrogen peroxide stabilizer), 0.15% 5-amino-1H-tetrazole monohydrate (etch inhibitor), 8% citric acid (organic acid), 7% 2-amino-2-methyl-1-propanol (alcohol amine), 0.5% polyethylene glycol (surfactant), 1.8% ammonium dihydrogen phosphate (inorganic hydrogen phosphate), 1.2% phosphoric acid (inorganic acid), and the balance deionized water.

The preparation method of the copper-aluminum film etching solution comprises the following steps: dissolving the components of the etching solution in deionized water, and stirring and dissolving for 1.5 to 3 hours at the temperature of 15 to 30 ℃ and at the speed of 150 to 800 revolutions per minute until a clear, transparent and uniform mixed solution is formed.

Example II,

The embodiment provides a copper-aluminum film etching solution, which comprises the following components in percentage by weight relative to the total weight of the etching solution: 6.3% hydrogen peroxide, 0.5% phenylurea (hydrogen peroxide stabilizer), 0.15% 5-amino-1H-tetrazole monohydrate (etch inhibitor), 8% citric acid (organic acid), 7% 2-amino-2-methyl-1-propanol (alcohol amine), 0.5% polyethylene glycol (surfactant), 1.8% ammonium dihydrogen phosphate (inorganic hydrogen phosphate), 1.2% phosphoric acid (inorganic acid), 0.05% ammonium fluoride (fluoride) and the balance deionized water.

The preparation method of the copper-aluminum film etching solution comprises the following steps: dissolving the components of the etching solution in deionized water, and stirring and dissolving for 1.5 to 3 hours at the temperature of 15 to 30 ℃ and at the speed of 150 to 800 revolutions per minute until a clear, transparent and uniform mixed solution is formed.

The effects of the etching solutions according to the examples of the present application will be specifically described below with reference to experiments.

1. Experiment on etching effect of etching solution

Experiment one: the etching solution (without fluorine) provided in the first embodiment is applied to a copper-aluminum laminated structure (copper film thickness)Thickness of aluminum film) The LCD-TFT glass substrate is etched, wherein the pH value of the etching solution is about 3.8, the etching temperature is 32 DEG CAnd respectively etching to different times (30 seconds, 40 seconds, 50 seconds, 60 seconds, 70 seconds, 80 seconds, 90 seconds, 100 seconds, 110 seconds and 120 seconds) and taking out, washing for 10 to 30 seconds by using deionized water, and then drying by blowing, and carrying out scanning electron microscope experiments on the LCD-TFT glass substrate etched to different times.

Experiment two: the etching solution (without fluorine) provided in the first example was applied to a copper-molybdenum laminated structure (copper film thickness)Thickness of molybdenum film) The LCD-TFT glass substrate is etched, wherein the pH value of the etching solution is about 3.8, the etching temperature is 32 ℃, the etching solution is etched for different time (30 seconds, 40 seconds, 50 seconds, 60 seconds, 70 seconds, 80 seconds, 90 seconds, 100 seconds, 110 seconds and 120 seconds) respectively and taken out, the etching solution is washed for 10 to 30 seconds by deionized water and then dried by air, and the LCD-TFT glass substrate etched for different time is subjected to scanning electron microscope experiments.

Experiment three: the etching solution (with fluorine) provided in the second embodiment was applied to a copper-aluminum laminated structure (copper film thickness)Thickness of aluminum film) The LCD-TFT glass substrate is etched, wherein the pH value of the etching solution is about 3.8, the etching temperature is 32 ℃, the etching solution is etched for different time (30 seconds, 40 seconds, 50 seconds, 60 seconds, 70 seconds, 80 seconds, 90 seconds, 100 seconds, 110 seconds and 120 seconds) respectively and taken out, the etching solution is washed for 10 to 30 seconds by deionized water and then dried by air, and the LCD-TFT glass substrate etched for different time is subjected to scanning electron microscope experiments.

The experimental results are as follows:

through experiments, it is found that the etching solution (free of fluorine) provided in the first embodiment of the present application has a good etching effect on a copper aluminum film, complete etching can be achieved within 60 seconds, the etching process is stable, the etching angle (taperangle) is 41.1 degrees (as shown in fig. 1), the critical dimension loss (CD loss) is 0.55 microns (as shown in fig. 1), no undercut (as shown in fig. 1), and no metal residue is left after etching (as shown in fig. 2).

Through a second experiment, it is found that the etching solution (without fluorine) provided in the first embodiment of the present application etches the copper molybdenum film, and when the etching is performed for 60 seconds, there is still metal residue (as shown in fig. 3), and no metal residue exists until the etching is performed for 100 seconds, and when the etching is performed for 100 seconds, the etching angle is 52.2 degrees, the critical dimension loss is 0.45 micrometers, and there is no undercut, so that the etching rate of the etching solution for the copper molybdenum film is lower than that for the copper aluminum film, that is, the etching solution in the first embodiment of the present application has a better etching effect for the copper aluminum film than for the copper molybdenum film.

Through the third experiment, the etching angle and the critical dimension loss after the etching of the copper-aluminum film by the etching solution (with fluorine) provided by the second embodiment of the application are very similar to those after the etching of the copper-aluminum film by the etching solution (without fluorine) provided by the first embodiment, and only about 50 seconds is needed for the etching of the copper-aluminum film by the etching solution (with fluorine) provided by the second embodiment until no metal remains, so that the etching rate is higher than that of the etching solution (without fluorine) provided by the first embodiment.

2. Experiment on service life

Laminating copper and aluminum (thickness of copper film)Thickness of aluminum film) The LCD-TFT glass substrate with the structure is cut into a plurality of small pieces for standby, the small pieces are etched by using the etching solution provided by the implementation of one implementation under different copper ion contents respectively, the etching temperature is 32 ℃, the environment with different copper ion contents in the etching solution is simulated by adding different amounts of nano copper powder into the etching solution, and the total adding amount of the nano copper powder is sequentially set to be 0.001 g/ml (1000ppm), 0.002 g/ml (2000ppm), 0.003 g/ml (3000ppm), 0.004 g/ml (4000ppm), 0.005 g/ml (5000ppm), 0.006 g/ml (6000ppm), 0.007 g/ml (7000ppm), 0.008 g/ml (8000 pp) and the likem), 0.009 g/ml (9000ppm), 0.010 g/ml (10000ppm), 0.011 g/ml (11000ppm), 0.012 g/ml (12000ppm), 0.013 g/ml (13000ppm) and 0.014 g/ml (14000ppm), wherein the nano-copper powder is added by adding 0.001 g/ml (1000ppm) of nano-copper powder to the etching solution provided in the first example before etching, dissolving for more than 15 minutes and raising the temperature to 32 ℃ for etching, and then adding 0.001 g/ml (1000ppm) of nano-copper powder every 120 seconds during etching until the total addition of the nano-copper powder set by the corresponding experiment is achieved.

As a result, the etching effect of the etching solution provided by the present embodiment can still satisfy the etching requirement when the copper ion concentration is added to 0.012 g/ml (12000ppm), and the etching efficiency is significantly reduced when the copper ion concentration is added to 0.013 g/ml (13000ppm), so that the etching solution provided by the present embodiment can be used until the copper ion concentration is 0.012 g/ml (12000ppm), and therefore, the etching solution provided by the present embodiment has a longer service life.

The embodiment of the application can ensure the stability of etching quality by matching hydrogen peroxide with a chelating agent, an inhibitor, a stabilizer, inorganic phosphate or inorganic hydrogen phosphate, inorganic acid and a surfactant, so that the etching process is stable, the etching rate is moderate, the etching angle is proper, no metal residue and no undercut are left after etching, and the requirements of 2000-8000 angstrom thick copper film and 100-400 angstrom thick aluminum film production line can be met for the etching of the copper-aluminum laminated film. The etching solution in the embodiment of the application is a dosage type etching solution, and can be directly used until the concentration of copper ions is 0.012 g/ml (12000ppm) without adding additives or a sub-solution to supplement components in the etching process, so that the etching solution has a long service life. The content of hydrogen peroxide in the etching solution is lower, so that the phenomenon that the hydrogen peroxide content is too high to cause bumping can be avoided, the safety of the etching solution is improved, the cost is low, and the industrial application is facilitated. In addition, the etching solution can also have a better etching effect without adding fluoride, and even if the fluoride is added, only the fluoride with extremely low content is needed, so that the substrate glass cannot be damaged.

The copper-aluminum film etching solution provided by the embodiment of the present application is described in detail above, and the principle and the embodiment of the present application are explained by applying specific examples herein, and the description of the above embodiment is only used to help understanding the method and the core concept of the present application; meanwhile, for those skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.