Anti-crystallization copper etching solution and preparation method and application thereof

Abstract

The application belongs to the technical field of etching liquid, and particularly relates to an anti-crystallization copper etching liquid and a preparation method and application thereof. The copper etching liquid is obtained by mixing hydrogen peroxide, inorganic acid, organic acid, fluorine compound, hydrogen peroxide stabilizer, organic sulfonic acid sodium salt, pyrazine polycarboxylic acid, amino acid ionic liquid and water. The components in the copper etching liquid jointly act, so that the phase stability of the copper etching liquid is significantly improved, the copper etching liquid can avoid crystallization in long-time work, and is suitable for industrial application.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of etching solution, and particularly relates to an anti-crystallization copper etching solution and a preparation method and application thereof. BACKGROUND

[0002] In the process of LCD, OLED, Mini / Micro LED and other display panels, micron / submicron processing of copper conductive lines through wet process is a key link. In the wet process, the cost of the copper etching process accounts for about 15%-20% of the total cost, and the loss of defective products caused by the quality of the copper etching process accounts for more than 30% of the total defective rate. Therefore, the copper etching process is of great significance to the yield and cost control of the industry.

[0003] In the copper etching process, the copper etching solution is a key medium for realizing fine processing, and its performance directly determines the line width, line spacing and edge roughness of the processed line, thereby affecting the display performance and the transmission efficiency of the panel driving signal. The existing copper etching solution is prone to crystallization and precipitation of solutes (copper complexes and sulfate salts) during work.

[0004] For example, patent CN118773612A discloses a kind of etching solution composition for composite copper film, and the etching solution is composed of hydrogen peroxide, hydrofluoric acid, sodium dihydrogen phosphate, complexing agent, diethyl succinate, hydantoin, potassium bisulfate, corrosion inhibitor, imino diacetic acid, organic alcohol and water. The complexing agent is disodium ethylenediaminetetraacetate and diethylenetriamine pentamethylene phosphonate. Disodium ethylenediaminetetraacetate and diethylenetriamine pentamethylene phosphonate can form a complex with copper ions dissolved in the etching process through chelation, thereby ensuring the stability of the copper etching solution. However, when the etching solution is used in the production line for a long time, the flow channel of the etching machine is complex, and the areas such as the corner of the reflux tank and the outlet of the buffer tank are prone to form liquid accumulation zones. After the static enrichment of copper ions, they are mixed into the main circulation with the start / stop of the equipment and the flow fluctuation, which leads to an abnormal increase in the overall copper ion concentration. At the same time, the negative pressure exhaust of the etching workshop causes the slow evaporation of water in the spray chamber, which indirectly increases the concentration of solutes (copper complexes and sulfate salts). These factors can cause the copper complexes or sulfate salts in the etching solution to reach a supersaturated state and crystallize and precipitate. The crystalline particles not only weaken the etching effect of the etching solution, but also block the spray nozzles of the etching machine and cause crystalline accumulation, which requires frequent shutdown for cleaning, reduces the production efficiency, and damages the equipment.

[0005] Therefore, it is necessary to provide a new copper etching solution to solve the problem of easy crystallization of existing copper etching solutions. SUMMARY

[0006] To solve the above technical problems, one of the purposes of the present application is to provide an anti-crystallization copper etching solution.

[0007] The technical solution adopted by the present application is as follows:

[0008] An anti-crystalline copper etching solution, comprising, in percentage by mass: hydrogen peroxide 10-25%, inorganic acid 1-10%, organic acid 0.1-5%, fluorine compound 0.5-0.9%, hydrogen peroxide stabilizer 0.5-1%, organic sulfonic acid sodium salt 1-3%, pyrazine polycarboxylic acid 0.1-1%, amino acid ionic liquid 0.1-5%, and the rest is water.

[0009] Preferably, the amount of hydrogen peroxide is not limited to 10%, 12%, 14%, 15%, 18%, 20%, 22%, 24%, or 25%.

[0010] Preferably, the inorganic acid is at least one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and boric acid. The amount of inorganic acid is not limited to 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%.

[0011] Preferably, the organic acid is at least one of citric acid, malic acid, tartaric acid, lactic acid, salicylic acid, fumaric acid, gluconic acid, succinic acid, 2-hydroxyethyl phosphonic acid, and 2-hydroxyethanesulfonic acid. The amount of organic acid is not limited to 0.1%, 0.3%, 0.5%, 1%, 2%, 2.5%, 3%, 3.8%, 4%, or 5%.

[0012] Preferably, the fluorine compound is at least one of hydrogen fluoride, fluoroboric acid, and ammonium hydrogen fluoride. The amount of fluorine compound is not limited to 0.5%, 0.6%, 0.7%, 0.8%, or 0.9%.

[0013] Preferably, the hydrogen peroxide stabilizer is composed of hydroxyethyl urea and N-oleyl propylene diamine mixed in a mass ratio of (2-5) : 1. The amount of hydrogen peroxide is not limited to 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%.

[0014] Preferably, the organic sulfonic acid sodium salt is at least one of sodium sulfosuccinate, sodium fatty alcohol ether sulfonate, sodium xylene sulfonate, disodium 2,6-naphthalene disulfonate, sodium alpha-methyl styrene sulfonate, and sodium lignosulfonate. The amount of organic sulfonic acid sodium salt is not limited to 1%, 1.2%, 1.5%, 1.8%, 2%, 2.3%, 2.6%, 2.9%, or 3%.

[0015] Preferably, the pyrazine polycarboxylic acid is at least one of pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, pyrazine-2,6-dicarboxylic acid, pyrazine-2,3,5-tricarboxylic acid, pyrazine-2,3,6-tricarboxylic acid, and pyrazine-2,3,5,6-tetracarboxylic acid. The amount of pyrazine polycarboxylic acid is not limited to 0.1%, 0.2%, 0.3%, 0.5%, 0.7%, 0.9%, or 1%.

[0016] Preferably, the amino acid ionic liquid is at least one of 1-butyl-3-methylimidazolium threonine salt, 1-ethyl-3-methylimidazolium arginine salt, 1-butyl-3-methylimidazolium alanine salt, 1-ethyl-3-methylimidazolium glycine salt, 1-hydroxyethyl-3-methylimidazolium lysine salt. The amount of the amino acid ionic liquid is not limited to 0.1%, 0.3%, 0.6%, 1%, 2%, 2.8%, 3%, 3.5%, 4%, 5%.

[0017] In the above formula, the organic sulfonic acid sodium salt has both dispersion and solubilization functions, not only provides an organic sulfonic acid group, and the hydrophobic group thereof can be inserted into the interstitial space of the copper complex or copper salt crystal lattice, destroy the regularity of the crystal lattice, and improve the solubility of the copper complex or copper salt crystal; and also provides sodium ions, which can be used as a control ion in the system, and are adsorbed on the surface of the critical crystal nucleus of the copper complex or copper salt through physical or chemical action, on the one hand, to improve the energy barrier of crystal nucleation, and inhibit the spontaneous formation and growth of the crystal nucleus; on the other hand, after the adsorption of the sodium ions, the wettability and charge distribution of the crystal nucleus surface are changed, the aggregation driving force between the crystal nuclei is weakened, and the crystallization precipitation and particle growth are further blocked.

[0018] The molecular structure of the pyrazine polycarboxylic acid is planar and rigid, and when the copper complex or copper salt has a crystallization nucleation tendency, it can be adsorbed on the active site of the crystalline lattice, replace the original molecules in the lattice, cause lattice distortion and increase defects, increase the activation energy of crystal growth, inhibit the nucleation process in the early stage of crystallization, and it is difficult to form crystal particles. In addition, the pyrazine polycarboxylic acid molecule contains multiple carboxyl groups and a pyrazine ring, and both the carboxyl groups and the nitrogen atom of the pyrazine ring can form coordination bonds with copper ions, and together with the amino acid ionic liquid, they coordinate with copper ions to form a mixed ligand complex, so that the saturation carrying concentration of the etching solution for copper ions is improved, and even if the copper ions accumulate for a long time, it is difficult to reach a supersaturated state. At the same time, the imidazole cation group of the amino acid ionic liquid has hydrophilicity, and can form a hydration layer on the surface of the complex molecule, hinder the aggregation between copper complex molecules through hydrogen bonds and hydrophobic interaction, and avoid the formation of large-size aggregates.

[0019] The combination of hydroxyethyl urea and N-oleyl propylenediamine as a hydrogen peroxide stabilizer has a synergistic effect, effectively avoids the decrease in etching rate caused by the rapid decomposition of hydrogen peroxide, reduces the local enrichment caused by insufficient dissolution of copper ions, and further avoids the co-precipitation of impurities and copper ions to form crystals.

[0020] The second object of the present application is to provide a preparation method of the anti-crystallization copper etching solution as described above. Hydrogen peroxide, inorganic acid, organic acid, fluorine compound, hydrogen peroxide stabilizer, organic sulfonic acid sodium salt, pyrazine polycarboxylic acid and amino acid ionic liquid are added to water according to the required proportion of the copper etching solution, mixed and dissolved, and then the anti-crystallization copper etching solution is obtained.

[0021] Preferably, a filtration step is also performed after dissolution to remove part of the undissolved solids that can be present.

[0022] A third object of the present application is to provide an application of the anti-crystallization copper etching solution in etching Cu / MTD substrates.

[0023] The present application has the following advantages:

[0024] A brand new copper etching solution formula is provided, which is prepared from hydrogen peroxide, inorganic acid, organic acid, fluorine compound, hydrogen peroxide stabilizer, organic sulfonic acid sodium salt, pyrazine polycarboxylic acid and amino acid ionic liquid and water as raw materials, and through the regulation of the proportion of the amount, an anti-crystallization copper etching solution is obtained. The copper etching solution has remarkable phase stability, can avoid the precipitation of crystals in a long time work, and is suitable for industrial application. Moreover, the copper etching solution has excellent etching performance, the CD bias (critical dimension bias) can be maintained between 1±0.1 μm, the etching cone angle is stable between 41-44°, the etching is efficient and safe, and can well meet the etching requirements of Cu / MTD composite layer. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 The crystallization condition comparison chart of the copper etching solution prepared for Example 1 and Comparative Example 2, in which (a) is the appearance of the copper etching solution prepared in Example 1 at 32 hours, and (b) is the appearance of the copper etching solution prepared in Comparative Example 2 at 32 hours.

[0026] Figure 2 The schematic diagram for observing the crystallization precipitation of the copper etching solution under an optical microscope (20x), in which (a) is the result of the copper etching solution prepared in Example 1 at 32 hours, and no crystallization precipitation is observed, and (b) is the result of the copper etching solution prepared in Comparative Example 2 at 16 hours, and crystallization precipitation can be observed; the white part in the figure is a bubble.

[0027] Figure 3 The SEM diagram of the etching effect of the copper etching solution prepared in Example 1 of the present application, in which 1 is CD bias, and 2 is cone angle.

[0028] Figure 4 The SEM diagram of the etching effect of the copper etching solution prepared in Example 2 of the present application, in which 1 is CD bias, and 2 is cone angle.

[0029] Figure 5 The SEM diagram of the etching effect of the copper etching solution prepared in Example 3 of the present application, in which 1 is CD bias, and 2 is cone angle.

[0030] Figure 6SEM images of etching effect of copper etching solution prepared for the present application comparative example 1, on the figure: 1 for CD bias, 2 for taper angle.

[0031] Figure 7 SEM images of etching effect of copper etching solution prepared for the present application comparative example 2, on the figure: 1 for CD bias, 2 for taper angle.

[0032] Figure 8 SEM images of etching effect of copper etching solution prepared for the present application comparative example 3, on the figure: 1 for CD bias, 2 for taper angle.

[0033] Figure 9 SEM images of etching effect of copper etching solution prepared for the present application comparative example 4, on the figure: 1 for CD bias, 2 for taper angle.

[0034] Figure 10 SEM images of etching effect of copper etching solution prepared for the present application comparative example 5, on the figure: 1 for CD bias, 2 for taper angle. DETAILED DESCRIPTION

[0035] For the convenience of understanding, the technical solutions of the present application are described in more detail below in conjunction with examples. Unless otherwise specified, the terms used herein have meanings commonly understood by those skilled in the art.

[0036] Example 1

[0037] A copper etching solution, comprising the following ingredients in mass percentage: hydrogen peroxide 10%, inorganic acid 10%, organic acid 0.1%, fluorine compound 0.9%, hydrogen peroxide stabilizer 0.8%, organic sulfonic acid sodium salt 1%, pyrazine polycarboxylic acid 0.1%, amino acid ionic liquid 0.1%, and the balance being water.

[0038] Among them, the inorganic acid is hydrochloric acid, the organic acid is citric acid, the fluorine compound is hydrogen fluoride, the hydrogen peroxide stabilizer is composed of hydroxyethyl urea and N-oil propylene diamine with a mass ratio of 2:1, the organic sulfonic acid sodium salt is sodium lignosulfonate, the pyrazine polycarboxylic acid is pyrazine-2,3-dicarboxylic acid, and the amino acid ionic liquid is 1-ethyl-3-methyl imidazole glycine salt.

[0039] The preparation method of the copper etching solution is as follows: hydrogen peroxide, inorganic acid, organic acid, fluorine compound, hydrogen peroxide stabilizer, organic sulfonic acid sodium salt, pyrazine polycarboxylic acid and amino acid ionic liquid are added to water, mixed and dissolved, and filtered to remove undissolved solids, thereby obtaining the copper etching solution.

[0040] Example 2

[0041] A copper etching solution comprises the following components in percentage by mass: hydrogen peroxide 18%, inorganic acid 5%, organic acid 2.5%, fluorine compound 0.7%, hydrogen peroxide stabilizer 0.5%, organic sulfonic acid sodium salt 2%, pyrazine polycarboxylic acid 0.5%, amino acid ionic liquid 3%, and the balance is water.

[0042] The inorganic acid is sulfuric acid, the organic acid is tartaric acid, the fluorine compound is fluoroboric acid, the hydrogen peroxide stabilizer is composed of hydroxyethyl urea and N-octylpropylenediamine with a mass ratio of 4:1, the organic sulfonic acid sodium salt is xylene sulfonic acid sodium salt, the pyrazine polycarboxylic acid is pyrazine-2,6-dicarboxylic acid, and the amino acid ionic liquid is 1-ethyl-3-methylimidazole arginine salt.

[0043] The preparation method is as follows: hydrogen peroxide, inorganic acid, organic acid, fluorine compound, hydrogen peroxide stabilizer, organic sulfonic acid sodium salt, pyrazine polycarboxylic acid, and amino acid ionic liquid are added into water, mixed and dissolved, and filtered to remove undissolved solids.

[0044] Example 3

[0045] A copper etching solution comprises the following components in percentage by mass: hydrogen peroxide 25%, inorganic acid 1%, organic acid 5%, fluorine compound 0.5%, hydrogen peroxide stabilizer 1%, organic sulfonic acid sodium salt 3%, pyrazine polycarboxylic acid 1%, amino acid ionic liquid 5%, and the balance is water.

[0046] The inorganic acid is nitric acid, the organic acid is succinic acid, the fluorine compound is ammonium hydrogen fluoride, the hydrogen peroxide stabilizer is composed of hydroxyethyl urea and N-octylpropylenediamine with a mass ratio of 5:1, the organic sulfonic acid sodium salt is 2,6-naphthalene disodium disulfonate, the pyrazine polycarboxylic acid is pyrazine-2,3,5,6-tetracarboxylic acid, and the amino acid ionic liquid is 1-hydroxyethyl-3-methylimidazole lysine salt.

[0047] The preparation method is as follows: hydrogen peroxide, inorganic acid, organic acid, fluorine compound, hydrogen peroxide stabilizer, organic sulfonic acid sodium salt, pyrazine polycarboxylic acid, and amino acid ionic liquid are added into water, mixed and dissolved, and filtered to remove undissolved solids.

[0048] Comparative Example 1

[0049] Comparative Example 1 and Example 1 have the same preparation method, except that equal mass of potassium lignosulfonate is used to replace sodium lignosulfonate.

[0050] Comparative Example 2

[0051] Comparative Example 2 and Example 1 have the same preparation method, except that equal mass of ethylenediaminetetraacetic acid is used to replace pyrazine-2,3-dicarboxylic acid.

[0052] Comparative Example 3

[0053] Comparative Example 3 was prepared in the same manner as Example 1, except that the same amount of glycine was used to replace 1-ethyl-3-methylimidazole glycinate.

[0054] Comparative Example 4

[0055] Comparative Example 4 was prepared in the same manner as Example 1, except that the hydrogen peroxide stabilizer was only hydroxyethyl urea.

[0056] Comparative Example 5

[0057] Comparative Example 5 was prepared in the same manner as Example 1, except that the hydrogen peroxide stabilizer was only N-oleyl propylene diamine.

[0058] Performance Test

[0059] 1. Phase stability evaluation

[0060] At room temperature, 6000 ppm copper powder was added to 100 mL of copper etching solution prepared in Examples 1-3 and Comparative Examples 1-5, and after being fully dissolved, 10 mL was taken and placed in a petri dish in a fume hood at room temperature, and the air speed of the fume hood was controlled at 0.5 m / s to simulate the production line environment. At 8 h, 16 h, 24 h and 32 h, a small amount of etching solution was taken and observed for crystal precipitation using an optical microscope (20x), as shown in the following table. When no crystal precipitation occurred, it was evaluated as “√”, and when crystal precipitation occurred, it was evaluated as “X”. The specific results are shown in Table 1. Figures 1-2

[0061] Table 1. Stability evaluation of copper etching solution prepared in Examples 1-3 and Comparative Examples 1-5

[0062] ;

[0063] As can be seen from Table 1, the copper etching solution obtained in Examples 1-3 can still maintain phase stability for a long time under the simulated production line environment, without crystal precipitation, and can meet the needs of the production line to the maximum extent.

[0064] ​Comparative Example 1 and Comparative Example 1 can be known that the copper etching solution of the present application uses sodium lignosulfonate, which can better inhibit the crystal precipitation than potassium lignosulfonate. Comparative Example 1 and Comparative Example 2 can be known that the copper etching solution of the present application uses pyrazine polycarboxylic acid, which can not only provide multiple coordination sites to form a complex with copper ions, but also can selectively insert the crystal lattice gap of copper salt impurities to destroy the lattice regularity and prevent the crystal precipitation than ethylenediaminetetraacetic acid. Comparative Example 1 and Comparative Example 3 can be known that the copper etching solution of the present application uses amino acid ionic liquid, which can better adjust the ionic strength of the etching solution, improve the uniformity of the etching solution and reduce the formation of crystal nuclei caused by local concentration difference than glycine. Comparative Example 1 and Comparative Example 4 and 5 can be known that the hydrogen peroxide stabilizer in the etching solution formula of the present application is a combination of hydroxyethyl urea and N-oil-based propylene diamine, which can effectively inhibit the abnormal decomposition of hydrogen peroxide and avoid the local supersaturation of copper ions caused by uneven decomposition, thereby to a certain extent, it is conducive to inhibiting the crystal precipitation.

[0065] 2. Performance evaluation

[0066] The performance of the copper etching solution prepared in Examples 1-3 and Comparative Examples 1-5 was tested.

[0067] 1) Etching effect evaluation

[0068] At 33℃, the Cu / MTD substrate (Cu / MTD=6500 / 150 Å) was etched using an etching machine, and the total etching time was 1.8 times EPD. EPD is the time required for the Cu / MTD substrate to become transparent during etching, that is, the etching end time. After etching, the Cu / MTD substrate was taken out, washed and dried, and then observed by scanning electron microscope (SEM) to observe the cone angle, CDbias (critical dimension bias, in this test, the amount of side etching at the bottom of the Cu metal film layer was used to represent), and the etching effect was evaluated.

[0069] 2) Safety evaluation of copper powder dissolution limit

[0070] The prepared copper etching solution was placed in a 33℃ water bath, 6000 ppm copper powder was added, and stirred until completely dissolved. Then, every time 1000 ppm copper powder was added, the change of etching solution temperature was continuously monitored within 1 hour after complete dissolution. If the etching solution temperature rises sharply, it means that the internal balance of the etching solution cannot be maintained. The maximum content of copper powder contained in the etching solution at this time was recorded to represent the safety of the etching solution, and the higher the maximum content of copper powder, the better the safety.

[0071] The test results are shown in Table 2 and Figures 3-10 .

[0072] Table 2 Etching effect of copper / MTD substrate

[0073] ;

[0074] Figures 3-10 Etching effect of copper etching liquid prepared according to Examples 1-3 and Comparative Examples 1-5, respectively.

[0075] It can be seen from Table 2 and Figures 3-10 It can be seen from Table 2 and

[0076] It can be seen from Comparative Example 1 and Comparative Example 1 that the sodium salt of organic sulfonic acid used in the present application has a larger radius of sodium ion than potassium ion, and the wetting effect of the etching liquid is better, and the etching effect is better. It can be seen from Comparative Example 1 and Comparative Example 2 that the complexing rate of ethylenediaminetetraacetic acid to copper ions is too fast, which leads to excessive longitudinal etching and a smaller taper angle. It can be seen from Comparative Example 1 and Comparative Example 3 that the amino acid ionic liquid used in the present application has a synergistic effect between the imidazole ring and the amino acid side chain, which can better regulate the taper angle and line width precision. It can be seen from Comparative Example 1 and Comparative Examples 4 and 5 that the hydrogen peroxide stabilizer used in the present application is a combination of hydroxyethyl urea and N-oleyl propylene diamine, and the combination of the two can not only improve the safety of the etching liquid, but also ensure the etching precision and stability.

[0077] The above test results show that the copper etching liquid provided by the present application has good phase stability and safety, and can be widely used in the field of display panel etching.

[0078] The above embodiments are only used to illustrate the technical solutions of the present application, and are not intended to limit the present application; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that any modification, equivalent replacement and improvement made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. An anti-crystallization copper etching solution, characterized in that, The composition, by mass percentage, includes: 10-25% hydrogen peroxide, 1-10% inorganic acid, 0.1-5% organic acid, 0.5-0.9% fluorine compound, 0.5-1% hydrogen peroxide stabilizer, 1-3% sodium organic sulfonate, 0.1-1% pyrazine polycarboxylic acid, 0.1-5% amino acid ionic liquid, with the balance being water; the hydrogen peroxide stabilizer is composed of hydroxyethyl urea and N-oleopropyl diamine mixed in a mass ratio of (2-5):

1.

2. The anti-crystallization copper etching solution as described in claim 1, characterized in that, The inorganic acid is at least one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and boric acid.

3. The anti-crystallization copper etching solution as described in claim 1, characterized in that, The organic acid is at least one of citric acid, malic acid, tartaric acid, lactic acid, salicylic acid, fumaric acid, gluconic acid, succinic acid, 2-hydroxyethylphosphonic acid, and 2-hydroxyethanesulfonic acid.

4. The anti-crystallization copper etching solution as described in claim 1, characterized in that, The fluorine compound is at least one of hydrogen fluoride, fluoroboric acid, and ammonium hydrogen fluoride.

5. The anti-crystallization copper etching solution as described in claim 1, characterized in that, The organic sulfonate sodium salt is at least one of sodium dioctyl sulfosuccinate, sodium fatty alcohol ether sulfonated succinate, sodium xylene sulfonate, disodium 2,6-naphthalene disulfonate, sodium α-methylstyrene sulfonate, and sodium lignin sulfonate.

6. The anti-crystallization copper etching solution as described in claim 1, characterized in that, The pyrazine polycarboxylic acid is at least one of pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, pyrazine-2,6-dicarboxylic acid, pyrazine-2,3,5-tricarboxylic acid, pyrazine-2,3,6-tricarboxylic acid, and pyrazine-2,3,5,6-tetracarboxylic acid.

7. The anti-crystallization copper etching solution as described in claim 1, characterized in that, The amino acid ionic liquid is at least one of 1-butyl-3-methylimidazolium threonine, 1-ethyl-3-methylimidazolium arginine, 1-butyl-3-methylimidazolium alanine, 1-ethyl-3-methylimidazolium glycine, and 1-hydroxyethyl-3-methylimidazolium lysine.

8. A method for preparing an anti-crystallization copper etching solution as described in any one of claims 1-7, characterized in that, According to the required proportions of the copper etching solution, hydrogen peroxide, inorganic acid, organic acid, fluorine compound, hydrogen peroxide stabilizer, sodium organic sulfonate, pyrazine polycarboxylic acid and amino acid ionic liquid are added to water and mixed and dissolved to obtain the solution.

9. The application of an anti-crystallization copper etchant as described in any one of claims 1-7 in etching Cu / MTD substrates.

Images