Copper / molybdenum thin film etching solution of non-hydrogen peroxide system, preparation method of copper / molybdenum thin film etching solution and etching method of copper / molybdenum thin film

Abstract

The invention relates to the technical field of etching liquid, in particular to copper / molybdenum thin film etching liquid of a non-hydrogen peroxide system, a preparation method of the copper / molybdenum thin film etching liquid and an etching method of a copper / molybdenum thin film. The copper / molybdenum film etching liquid comprises the following raw materials: 5.00 wt%-15.00 wt% of peroxysuccinic acid, 0.80 wt%-2.30 wt% of an acidic material, 0.10 wt%-1.00 wt% of a corrosion inhibitor, 1.00 wt%-5.00 wt% of a peroxysuccinic acid stabilizer and the balance of water. The etching liquid belongs to a non-hydrogen peroxide system and does not contain hydrogen peroxide, so that the consumption of acidic substances, complexing agents and other substances can be reduced on the basis of realizing the oxidability of hydrogen peroxide and avoiding interference byproducts, and the production cost and the recovery difficulty are reduced. Meanwhile, the etching liquid has the durability of the service life and the good performance of the etching morphology.

Description

Technical Field

[0001] The present invention relates to the technical field of etching solutions, and in particular, to a copper / molybdenum thin film etching solution without a hydrogen peroxide system, a preparation method thereof, and an etching method for copper / molybdenum thin films. Background Art

[0002] Etching is to transfer the photoresist pattern obtained by photolithography onto the thin film on the surface of the wafer, that is, by using the covering and protection effects of the photoresist film, to remove the thin film without photoresist protection by means of chemical reaction or physical action to complete the pattern transfer. Sometimes metal thin films are used in the etching process, such as pure metal film layers of Cu, Al, and Mo, etc., and composite metal film layers such as Cu / Mo and Mo / Al / Mo can also be used.

[0003] For the above-mentioned metal thin films, especially copper-containing thin films, etching solutions containing a hydrogen peroxide system are often used for etching. When using hydrogen peroxide to form an etching solution, more acidic substances and complexing agents and other materials need to be added to the etching solution to ensure the stability and etching ability of the etching solution. However, after adding too many acidic substances and complexing agents, the etching rate will increase significantly when the service life of the etching solution is relatively high, and then the etching morphology will be affected. At the same time, adding too many acidic substances and complexing agents also increases the production cost and recycling difficulty of the etching solution. Therefore, there is an urgent need for a new etching solution system to replace the hydrogen peroxide system, and at the same time, this new etching system can provide a sufficient acidic environment, complexing ability, oxidation ability, and no interfering by-products, etc.

[0004] In view of this, the present invention is specifically proposed. Summary of the Invention

[0005] The purpose of the present invention is to provide a copper / molybdenum thin film etching solution without a hydrogen peroxide system, a preparation method thereof, and an etching method for copper / molybdenum thin films. An embodiment of the present invention provides a new etching solution, which belongs to a non-hydrogen peroxide system. This etching solution does not contain hydrogen peroxide, and on the basis of realizing the oxidation ability of hydrogen peroxide and no interfering by-products, it reduces the dosage of substances such as acidic substances and complexing agents, and reduces the production cost and recycling difficulty. At the same time, this etching solution takes into account the durability of the service life and the good etching morphology.

[0006] The present invention is implemented as follows:

[0007] An embodiment of the present invention describes a copper / molybdenum thin film etching solution without a hydrogen peroxide system. In terms of mass percentage, the raw materials of this copper / molybdenum thin film etching solution include: 5.00 wt% - 15.00 wt% of peroxosuccinic acid, 0.80 wt% - 2.30 wt% of acidic materials, 0.10 wt% - 1.00 wt% of corrosion inhibitors, 1.00 wt% - 5.00 wt% of peroxosuccinic acid stabilizers, and the balance is water.

[0008] The succinic peroxide used in the embodiments of the present invention can simultaneously provide oxidation ability, acidic environment and complexing ability, thereby enabling the copper / molybdenum thin film etchant to improve its service life without the need to additionally add a complexing agent, and having a good etching morphology.

[0009] The embodiments of the present invention describe a preparation method of a copper / molybdenum thin film etchant for a non-hydrogen peroxide system, including: mixing succinic peroxide, acidic materials, corrosion inhibitors, succinic peroxide stabilizers and water in proportion.

[0010] The preparation method provided by the embodiments of the present invention is simple to operate and easy to implement.

[0011] The embodiments of the present invention describe an etching method for a copper / molybdenum thin film, including: etching the copper / molybdenum thin film with the copper / molybdenum thin film etchant for a non-hydrogen peroxide system described in the foregoing embodiment.

[0012] This method can effectively etch the copper / molybdenum thin film, and as the concentration of metal ions increases, the etching rate and etching morphology remain stable.

[0013] The present invention has the following beneficial effects: The embodiments of the present invention provide an etchant that does not contain hydrogen peroxide. By selecting raw materials and determining the ratio, it is ensured that the etchant can etch the copper / molybdenum thin film. At the same time, the use of acidic components and complexing agents in the etchant is reduced, reducing the production cost and recycling difficulty of the etchant. At the same time, the etchant has a relatively high service life, and as the concentration of metal ions in the etchant increases, the stability of the etching rate and etching morphology can be ensured. Description of the Drawings

[0014] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the present invention, and therefore should not be regarded as limiting the scope. For those of ordinary skill in the art, without creative efforts, other related drawings can also be obtained based on these drawings.

[0015] Figure 1 SEM cross-sectional view of the etching with the etchant of Example 2 at Cu 0 ppm;

[0016] Figure 2 SEM cross-sectional view of the etching with the etchant of Example 2 at Cu 2000 ppm;

[0017] Figure 3 SEM cross-sectional view of the etching with the etchant of Example 2 at Cu 4000 ppm;

[0018] Figure 4SEM cross-sectional view etched by the etchant of Example 2 at 6000 ppm Cu;

[0019] Figure 5 SEM surface view etched by the etchant of Example 2 at 8000 ppm Cu. Detailed implementation manners

[0020] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely below. For those not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. For reagents or instruments not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0021] For the etching of copper / molybdenum thin films, in order to meet the high service life of the etchant, more acidic substances and complexing agents need to be added to the etchant for etching copper / molybdenum thin films. However, as the service life increases, that is, the concentration of metal ions increases, it will lead to an increase in the etching rate, resulting in a deterioration of the etching morphology, such as an increase in the cone angle and an increase in the unilateral etching amount. Therefore, for the hydrogen peroxide-based etchant, it is necessary to separately adjust the dosages of acidic substances and complexing agents through a large number of experiments to balance the durability of the service life and the good etching morphology, which increases the workload of researchers. And it also increases the production cost of the etchant.

[0022] Based on the above problems, the embodiments of the present invention disclose a copper / molybdenum thin film etchant of a non-hydrogen peroxide system. In terms of mass percentage, the raw materials of the copper / molybdenum thin film etchant include: 5.00 wt% - 15.00 wt% of peroxosuccinic acid, 0.80 wt% - 2.30 wt% of acidic materials, 0.10 wt% - 1.00 wt% of corrosion inhibitor, 1.00 wt% - 5.00 wt% of peroxosuccinic acid stabilizer, and the balance is water.

[0023] The embodiments of the present invention optimize the composition and dosage of the etchant, introduce peroxosuccinic acid to replace hydrogen peroxide, reduce the dosages of acidic substances and complexing agents, and can etch copper and molybdenum simultaneously. And as the metal ions increase, the stability of the etching rate can also be ensured, forming a good etching morphology.

[0024] Specifically, in terms of mass percentage, its raw materials include: 5.00wt%-15.00wt% of succinic peroxide, 0.30wt%-0.80wt% of acidic composition A, 0.50wt%-1.50wt% of acidic composition B, 0.10wt%-1.00wt% of corrosion inhibitor, 1.00wt%-5.00wt% of succinic peroxide stabilizer, and the balance is water. Preferably, its raw materials include: 8.00wt%-12.00wt% of the succinic peroxide, 0.30wt%-0.60wt% of the acidic composition A, 0.80wt%-1.50wt% of the acidic composition B, 0.30wt%-0.60wt% of the corrosion inhibitor, 1.00wt%-3.00wt% of the succinic peroxide stabilizer, and the balance is water.

[0025] Specifically, the copper / molybdenum thin film etching solution uses materials with succinic peroxide as the core, which contains peroxide groups to provide oxidation ability. At the same time, the acidity coefficient (pKa) of succinic peroxide is about 3.72, and the pH of its 5% aqueous solution is about 2.01, indicating that peroxysuccinic acid can also provide a large amount of free H + to dissolve metal oxides. And the carboxylate groups it contains can also complex metal ions. In summary, the succinic peroxide provided in the embodiments of the present invention can simultaneously provide oxidation ability, hydrogen ions (i.e., acidic environment) and complexing ability, thereby enabling the etching solution to not require the addition of an additional complexing agent and increasing the service life. That is to say, the content of the components used in the etching solution provided in the embodiments of the present invention is less than that of each component in the hydrogen peroxide system, and no complexing agent is required, further reducing the research and development difficulty and production cost.

[0026] Meanwhile, the embodiments of the present invention use succinic peroxide as the core material. If a mixture of hydrogen peroxide and succinic acid is used as the core material of the etching solution, the effects of the embodiments of the present invention cannot be achieved. The specific reasons are as follows: The solubility of succinic acid is theoretically only 5.8 g / 100 mL at 25 °C (at 25 °C, 5.8 g of succinic acid is dissolved in 100 ml of water). If the succinic peroxide in the etching solution provided by the embodiments of the present invention is changed to hydrogen peroxide and the other materials remain the same, the measured solubility of succinic acid is only 1.8 g / 100 mL (1.8 g of succinic acid is dissolved in 100 ml of the above hydrogen peroxide-based etching solution). It can be seen that the amount of succinic acid dissolved in this hydrogen peroxide-based etching solution is small, which in turn leads to a small amount of carboxylate in the etching solution containing succinic acid and hydrogen peroxide. Therefore, in order to increase the amount of carboxylate, other materials need to be added to the etching solution containing succinic acid and hydrogen peroxide to increase the solubility of succinic acid, ultimately resulting in a more complex composition of the formed etching solution. An overly complex composition may affect the effect of the etching solution and also increase the detection cost, R & D cost, and production cost. At the same time, the etching rate of this hydrogen peroxide-based etching solution containing low-concentration succinic acid is low and the copper dissolution ability is very poor (<4000 ppm). Therefore, hydrogen peroxide and succinic acid cannot be used in combination to achieve the purpose of reducing or replacing the content of other reagents, and it is even more impossible to achieve a stable etching rate and etching morphology.

[0027] Further, in the embodiments of the present invention, succinic peroxide is used as the main oxidant for copper, and its dosage is any value between 5.00 wt%, 8.00 wt%, 10.00 wt%, 12.00 wt%, and 15.00 wt%, such as 5.00 wt% - 15.00 wt%, and preferably 8.00 wt% - 12.00 wt%. When succinic peroxide is within the above range, the etching rate of the etching solution for the copper / molybdenum metal film is more stable, and the morphology after etching is more excellent. If the content of succinic peroxide is lower than 5.00 wt%, the oxidation ability of the etching solution for the metal is poor and the complexing ability is insufficient, and the total etching rate is too slow, which may lead to precipitation phenomena, etc. If its content is higher than 15.00 wt%, the total etching rate is too fast, and even after adding a corrosion inhibitor, there are defects in unstable safety.

[0028] The dosage of the acidic material provided by the embodiments of the present invention is any value between 0.80 wt%, 1.00 wt%, 1.20 wt%, 1.50 wt%, 1.80 wt%, 2.00 wt%, or 2.30 wt%, such as 0.80 wt% - 2.30 wt%.

[0029] In the embodiments of the present invention, two different acids, namely acidic composition A and acidic composition B, are used to form the acidic material. Specifically, the dosage of acidic composition A is any value between 0.30 wt% and 0.80 wt%, such as 0.30 wt%, 0.40 wt%, 0.50 wt%, 0.60 wt%, 0.70 wt%, and 0.80 wt%, and is preferably 0.30 - 0.60 wt%.

[0030] Acidic composition A is selected from organic acids, for example, including but not limited to at least one of malonic acid, citric acid, acetic acid, and oxalic acid.

[0031] The dosage of acidic composition B is any value between 0.50 wt% and 1.50 wt%, such as 0.50 wt%, 0.80 wt%, 0.90 wt%, 1.00 wt%, 1.10 wt%, 1.20 wt%, 1.30 wt%, 1.40 wt%, and 1.50 wt%, and is preferably 0.8 wt% - 1.50 wt%.

[0032] Acidic composition B is selected from inorganic acids; for example, including but not limited to at least one of nitric acid, sulfuric acid, and ammonium bisulfate.

[0033] The inorganic acid used in the embodiments of the present invention can completely ionize hydrogen ions in water, further providing an acidic environment and playing a role in stabilizing the pH. The organic acid used in the embodiments of the present invention does not completely ionize hydrogen ions in water. On the one hand, it can stabilize the pH of the etching solution, and at the same time, it can chelate some metal ions to achieve the purpose of improving the taper angle.

[0034] Furthermore, the mass ratio of acidic composition A to the acidic composition B is (1:2) - (1:5). Using the above mass ratio can ensure that the pH of the formed copper / molybdenum thin film etching solution is within an appropriate range, enabling the etching solution to etch both the copper thin film and the molybdenum-containing thin film simultaneously and ensuring the stability of the etching rate. At the same time, when the two are within the above preferred range, as the metal ion concentration increases, the pH is more stable and the etching morphology is better. If it exceeds this range, the etching rate will be too slow or too fast, and it will affect the reaction of the self-assembled film compound and the corrosion inhibitor.

[0035] Furthermore, the dosage of the corrosion inhibitor is any value between 0.10 wt% and 1.00 wt%, such as 0.10 wt%, 0.20 wt%, 0.30 wt%, 0.40 wt%, 0.50 wt%, 0.60 wt%, 0.70 wt%, 0.80 wt%, 0.90 wt% and 1.00 wt%, etc., and preferably 0.30 wt% - 0.60 wt%. When the corrosion inhibitor is within the above dosage range, the etching rate of the etching solution is relatively stable, which can effectively improve the service life of the etching solution. If the content of the above corrosion inhibitor is less than 0.10 wt%, the total etching rate is too fast, affecting the service life of the etching solution. If its content is higher than 1.00 wt%, the total etching rate is too slow to effectively etch the copper film and the molybdenum-containing film.

[0036] The corrosion inhibitor is selected from azole compounds; for example, it includes but is not limited to at least one of 1,2,3-benzotriazole, methylbenzotriazole, mercaptobenzothiazole, and 5-aminotetrazole. The corrosion inhibitor forms a protective film by adsorbing on the metal surface by reacting with metal oxides, and can etch both the copper film and the molybdenum-containing film simultaneously. Moreover, with the increase in the metal ion concentration, it can ensure the stability of the etching rate and good etching morphology.

[0037] The corrosion inhibitor is preferably 5-aminotetrazole, and its corrosion inhibition performance is better than that of other substances, which can further improve the morphology after etching and prevent problems such as chamfering and etching indentation.

[0038] Furthermore, the dosage of the peroxydisuccinic acid stabilizer is any value between 1.00 wt% and 5.00 wt%, such as 1.00 wt%, 2.00 wt%, 3.00 wt%, 4.00 wt% and 5.00 wt%, etc., and preferably 1.00 wt% - 3.00 wt%.

[0039] In the embodiments of the present invention, the above peroxydisuccinic acid stabilizer can chelate metal ions in the etching solution, thereby preventing the decomposition of peroxide ions in peroxydisuccinic acid and ensuring the safety and etching ability of the etching solution.

[0040] Furthermore, the peroxydisuccinic acid stabilizer is selected from polyacids, for example, it includes but is not limited to N-hydroxyethyl ethylenediamine triacetic acid, aminotrimethylenephosphonic acid, and hydroxyethylidene diphosphonic acid.

[0041] Further, the pH of the copper / molybdenum thin film etching solution is 1.8 - 2.5, such as any value between 1.8 and 2.5 like 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, and 2.5. If the pH value of the copper / molybdenum thin film etching solution is less than 1.8, it will inhibit the reaction between the corrosion inhibitor and metal oxide to form a protective film. As the concentration of metal ions increases, the etching rate of the etching solution will increase significantly, resulting in poor etching morphology. If the pH value of the copper / molybdenum thin film etching solution is greater than 2.5, the etching rate will decrease significantly, and as the concentration of metal ions increases, metal residues or precipitation may occur in the etching solution.

[0042] Further, the embodiments of the present invention describe a preparation method of a copper / molybdenum thin film etching solution without a hydrogen peroxide system, including: mixing succinic peroxide, acidic materials (such as acidic composition A and acidic B), a corrosion inhibitor, a succinic peroxide stabilizer, and water in proportion. This preparation method is simple to operate, enabling the prepared copper / molybdenum thin film etching solution to etch copper thin films and molybdenum-containing thin films simultaneously. As the concentration of copper metal ions increases, good etching morphology can be ensured.

[0043] Specifically, mix succinic peroxide, a succinic peroxide stabilizer, and deionized water in proportion, and then mix with the acidic composition A, the acidic composition B, and the corrosion inhibitor.

[0044] It should be noted that the copper / molybdenum thin film etching solution provided by the embodiments of the present invention can etch copper alloys, especially copper-molybdenum metal layers with copper thin films and molybdenum thin films, where the molybdenum thin film can be a pure molybdenum thin film or a molybdenum alloy thin film, such as a molybdenum-titanium alloy thin film or a molybdenum-niobium alloy thin film.

[0045] Further, the embodiments of the present invention describe an etching method for copper / molybdenum thin films, including etching the copper / molybdenum thin films with the above-mentioned copper / molybdenum thin film etching solution without a hydrogen peroxide system.

[0046] Among them, the copper / molybdenum thin film includes a copper thin film and a molybdenum-containing thin film. The copper thin film is a pure copper thin film, and the molybdenum-containing thin film can be a pure molybdenum thin film or a molybdenum alloy thin film. The thickness of the copper thin film is The thickness of the molybdenum-containing thin film is

[0047] The features and properties of the present invention will be further described in detail below in conjunction with embodiments.

[0048] Examples 1 - 12 and Comparative Examples 1 - 10

[0049] Examples 1 - 12 and Comparative Examples 1 - 10 respectively provide an etching solution. The composition of the etching solution and the dosage of each raw material are shown in Table 1 below. The preparation of the etching solution is to mix each raw material according to the ratio in Table 1.

[0050] Table 1 Composition and Dosage of Etchant (Unit: wt%)

[0051]

[0052]

[0053] Among them, in acidic composition A in Table 1: malonic acid; in acidic composition B: ammonium bisulfate; corrosion inhibitor A: 5-aminotetrazole; corrosion inhibitor B: 1,2,3-benzotriazole; peroxide succinic acid stabilizer: N-hydroxyethyl ethylenediamine triacetic acid.

[0054] Experimental Example 1

[0055] Transfer 10 kg of the etchants of Examples 1-12 and Comparative Examples 1-10 to the etching device. After the temperature of the etchant reaches 30 ± 0.1 °C, etch the copper-molybdenum thin film, where the thickness of the copper thin film in the copper-molybdenum thin film is The thickness of the molybdenum thin film is The total etching time is 1.5 times of EPD (the time when all copper and molybdenum are etched). After the etching is completed, rinse it with water within 2 seconds, dry the moisture on the surface, and evaluate the performance parameters after etching by scanning electron microscope (SEM). The results are shown in Table 2 and Table 3, and Figures 1-5 .

[0056] Table 2 Etching Performance Parameters of Etchant on Copper-Molybdenum Thin Film (Cone Angle Condition)

[0057]

[0058]

[0059] Among them, ○: Good [cone angle is 30-60°]; ▲: General [cone angle > 60° or < 30°];

[0060] ×: At this copper concentration, the temperature of the etchant rises sharply or there are precipitates, and it cannot be used and tested safely.

[0061] Table 3 Evaluation Results of Etching of Copper-Molybdenum Thin Film by Etchant (Unilateral Etching Amount)

[0062]

[0063] Among them, ×: At this copper concentration, the temperature of the etchant rises sharply or there are precipitates, and it cannot be used and tested safely.

[0064] As can be seen from Table 2, if the components exceed the range provided by the embodiments of the present invention, such as Comparative Examples 1-10, the cone angle cannot meet the requirements. According to the comparison of the results of Example 2 with those of Comparative Examples 1 and 2, the cone angle is improved by adjusting the dosage of peroxysuccinic acid. According to the comparison of the results of Example 2 with those of Comparative Examples 5 and 6, it can be shown that the cone angle is improved by adjusting the dosage of the appropriate acidic composition. Except for a few embodiments with a large angle in the case of a high copper life of 8000 ppm in the etching solution provided by the embodiments of the present invention, after selecting an appropriate weight ratio of the acidic composition, the cone angle is improved to a certain extent, but these few embodiments still meet the cone angle requirements.

[0065] As can be seen from Table 3, if the components exceed the range provided by the embodiments of the present invention, such as Comparative Examples 1-10, the unilateral etching amount cannot meet the requirements. Except for a few embodiments with a large angle in the case of a high copper life of 8000 ppm in the etching solution provided by the embodiments of the present invention, after selecting an appropriate weight ratio of the acidic composition, the change amount of the unilateral etching amount is improved to a certain extent.

[0066] Combining Table 2 and Table 3, it can be seen that the etching solution of the embodiments of the present invention uses peroxysuccinic acid to form the etching solution, which can reduce the dosage of acidic substances and complexing agents, thereby reducing the usage cost of complexing agents and acidic substances. At the same time, since the acidic substances and complexing agents are reduced, the complexity of the etching solution formulation is reduced, further reducing the component analysis and detection cost and pressure of the etching solution, and ensuring the goodness of the etching morphology.

[0067] Figure 1 It represents the SEM cross-sectional view of the etching with the etching solution of Example 2 at Cu 0 ppm. From Figure 1 it can be seen that after the etching of the metal copper-molybdenum alloy with the etching solution composition of this example, the cone angle is between 48-49° and is straight without bending, and the etching effect is very good.

[0068] Figure 2 It represents the SEM cross-sectional view of the etching with the etching solution of Example 2 at Cu 2000 ppm. From Figure 2 it can be seen that after the etching of the metal copper-molybdenum alloy with the etching solution composition of this example, the cone angle is between 47-48° and is straight without bending, and the etching effect is very good.

[0069] Figure 3 It represents the SEM cross-sectional view of the etching with the etching solution of Example 2 at Cu 4000 ppm. From Figure 3 it can be seen that after the etching of the metal copper-molybdenum alloy with the etching solution composition of this example, the cone angle is between 55-56° and is straight without bending, and the etching effect is very good.

[0070] Figure 4 It represents the SEM cross-sectional view of the etching with the etching solution of Example 2 at Cu 6000 ppm. FromFigure 4 It can be seen that after etching the metal copper-molybdenum alloy with the etching solution composition of this embodiment, the taper angle is between 53-54° and is straight without bending, and the etching effect is very good.

[0071] Figure 5 It represents the SEM surface diagram of the etching with the etching solution of this Example 2 at Cu 8000 ppm. From Figure 5 It can be seen that after etching the metal copper-molybdenum alloy with the etching solution composition of this embodiment, the taper angle is between 56-57° and there is no residue.

[0072] Experimental Example 2

[0073] An etching solution was formed according to the formula and dosage in Table 4 below, and etching was carried out to detect its maximum service life, taper angle and unilateral etching situation. The results are shown in Table 4.

[0074] Table 4 Composition and Test Results of the Etching Solution

[0075]

[0076] ×: The etching solution cannot dissolve copper / the taper angle is unqualified / the unilateral etching amount is unqualified.

[0077] According to Table 4, on the premise of ensuring high service life and qualified etching morphology, the peroxide succinic acid system formula (Example 13) has less dosage of each component and does not require a complexing agent compared with the hydrogen peroxide system formula (Comparative Example 16).

[0078] Experimental Example 3

[0079] An etching solution was formed according to the formula and dosage in Table 5 below, and etching was carried out to test the copper dissolution ability. The results are shown in Table 5.

[0080] Table 5 Copper Dissolution Ability of the Etching Solution

[0081]

[0082]

[0083] According to Table 5, if hydrogen peroxide and succinic acid are directly used as the core materials to form the etching solution, its etching rate is low and the copper dissolution ability is very poor (<4000 ppm). Therefore, it is impossible to use hydrogen peroxide and succinic acid in combination as the core materials to achieve the purpose of reducing or replacing the content of other reagents.

[0084] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A copper / molybdenum thin film etching solution for a non-hydrogen peroxide system, characterized in that In terms of mass percentage, its raw materials include: 5.00wt%-15.00wt% of succinic peroxide, 0.80wt%-2.30wt% of acidic material, 0.10wt%-1.00wt% of corrosion inhibitor, 1.00wt%-5.00wt% of succinic peroxide stabilizer, and the balance is water.

2. The copper / molybdenum thin film etching solution of the non-hydrogen peroxide system according to claim 1, characterized in that In terms of mass percentage, its raw materials include: 5.00wt%-15.00wt% of succinic peroxide, 0.30wt%-0.80wt% of acidic composition A, 0.50wt%-1.50wt% of acidic composition B, 0.10wt%-1.00wt% of corrosion inhibitor, 1.00wt%-5.00wt% of succinic peroxide stabilizer, and the balance is water; Preferably, its raw materials include: 8.00wt%-12.00wt% of the succinic peroxide, 0.30wt%-0.60wt% of the acidic composition A, 0.80wt%-1.50wt% of the acidic composition B, 0.30wt%-0.60wt% of the corrosion inhibitor, 1.00wt%-3.00wt% of the succinic peroxide stabilizer, and the balance is water.

3. The copper / molybdenum thin film etching solution of the non-hydrogen peroxide system according to claim 2, characterized in that, The mass ratio of the acidic composition A to the acidic composition B is (1:2)-(1:5).

4. The copper / molybdenum thin film etching solution of the non-hydrogen peroxide system according to claim 2, characterized in that, The pH of the copper / molybdenum thin film etching solution is 1.8-2.

5.

5. The copper / molybdenum thin film etching solution of the non-hydrogen peroxide system according to any one of claims 2-4, characterized in that, The copper / molybdenum thin film etching solution meets at least one of the following requirements; (1) The acidic composition A is selected from organic acids; (2) The acidic composition B is selected from inorganic acids; (3) The corrosion inhibitor is selected from azole compounds; (4) The succinic peroxide stabilizer is selected from polyacids.

6. The copper / molybdenum thin film etching solution of the non-hydrogen peroxide system according to any one of claims 2-4, characterized in that, The copper / molybdenum thin film etching solution meets at least one of the following requirements; (1) The acidic composition A is selected from at least one of malonic acid, citric acid, acetic acid, and oxalic acid; (2) The acidic composition B is selected from at least one of nitric acid, sulfuric acid, and ammonium bisulfate; (3) The corrosion inhibitor is selected from at least one of 1,2,3-benzotriazole, methylbenzotriazole, mercaptobenzothiazole, and 5-aminotetrazole; (4) The succinic peroxide stabilizer is selected from at least one of N-hydroxyethyl ethylenediamine triacetic acid, aminotrimethylenephosphonic acid, and hydroxyethylidene diphosphonic acid.

7. A preparation method of a copper / molybdenum thin film etching solution for a non-hydrogen peroxide system as described in claim 1, characterized in that, Include: Mix succinic peroxide, acidic material, corrosion inhibitor, succinic peroxide stabilizer, and water in proportion.

8. The preparation method according to claim 7, characterized in that, Include: Mix the succinic peroxide, the succinic peroxide stabilizer, and the water evenly, and then mix with acidic composition A, acidic composition B, and the corrosion inhibitor.

9. An etching method for copper / molybdenum thin films, characterized in that, Include: Etch the copper / molybdenum thin film with the copper / molybdenum thin film etching solution of the non-hydrogen peroxide system described in claim 1.

10. The etching method according to claim 9, wherein The copper / molybdenum thin film includes a copper thin film and a molybdenum-containing thin film, wherein the thickness of the copper thin film is The thickness of the molybdenum-containing thin film is

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