Etching liquid composition and use thereof

Abstract

The application discloses an etching liquid composition and application thereof, and the etching liquid composition comprises hydrogen peroxide, an etching inhibitor, an etching additive, a metal chelating agent and a hydrogen peroxide stabilizer. The etching liquid composition designed by the application contains the etching inhibitor, the etching additive and the metal chelating agent, has a fast etching rate and good etching rate stability, has excellent stability and safety, has a long service life, and the etching inhibitor, the etching additive and the metal chelating agent have a certain synergistic effect on the efficacy of increasing the etching rate.

Description

Technical Field

[0001] The invention belongs to the technical field of etching and relates to an etching liquid composition and application thereof. Background Art

[0002] Etching technology is a method of using photolithography to process thin precision metal products. Its basic principle is to utilize the photosensitivity of chemical photosensitive materials, evenly apply photosensitive materials on both sides of the base metal substrate, and use photolithography to accurately copy the shape of the grid on the film plate to the photosensitive layer mask on both sides of the metal substrate. The mask of the non-photosensitive part is removed by development, and the exposed metal part is directly sprayed and pressurized with the corrosive liquid in subsequent processing and etched away, finally obtaining the required geometric shape and high-precision size product.

[0003] CN114318343A discloses an etching solution and its application. The etching solution components include an oxidant, a stabilizer, and deionized water. The stabilizer includes a stabilizer A containing a phosphate group, a stabilizer B containing an organic phosphonic acid and its salt, and a stabilizer C containing a polybasic organic hydroxy acid and its salt. The phosphate group in the stabilizer A accounts for 0.3-8wt% of the etching solution, the stabilizer B accounts for 0.05-5wt% of the etching solution, and the stabilizer C accounts for 0.1-10wt% of the etching solution. The etching solution has good stability, but it has problems such as decomposition of hydrogen peroxide when the metal ion content increases, resulting in a reduced etching rate, a shortened etching solution life, and a large amount of etching solution used.

[0004] CN113106453A discloses an etching solution composition and its application. The etching solution composition comprises: hydrogen peroxide, fluoride, metal corrosion inhibitor, hydrogen peroxide stabilizer, metal complexing agent, inorganic salt and water. The mass ratio of the hydrogen peroxide, fluoride, metal corrosion inhibitor, hydrogen peroxide stabilizer, metal complexing agent and inorganic salt is (5-25):(0.01-0.5):(0.1-2):(1-5):(1-10):(0.01-6). The etching solution composition is well compatible with various film structures and materials, leaves no residue after etching, and has mild storage conditions. However, the etching solution composition uses a fluorine-based substrate and has problems such as corrosion of silicon dioxide films and glass substrates and environmental pollution.

[0005] In order to solve the corrosion and safety problems of current etching solutions, improve the etching rate of the etching solution, improve the stability of the etching solution and the stability of the etching rate, extend the service life of the etching solution, and reduce the cost, it is necessary to develop an etching solution composition. Summary of the Invention

[0006] In response to the deficiencies of the prior art and actual needs, the present invention provides an etching solution composition and its application, which solves the corrosiveness and safety problems of current etching solutions, improves the etching rate of the etching solution, improves the stability of the etching solution and the stability of the etching rate, extends the service life of the etching solution, and reduces costs.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides an etching solution composition, comprising hydrogen peroxide, an etching inhibitor, an etching additive, a metal chelating agent, and a hydrogen peroxide stabilizer.

[0009] The present invention creatively discovers that an etching solution composition containing three components, namely, an etching inhibitor, an etching additive, and a metal chelating agent, has excellent stability and safety, a long service life, a fast etching rate, and good etching rate stability, and the three components have a certain synergistic effect in the above-mentioned effects.

[0010] Preferably, the mass ratio of the hydrogen peroxide, the etching inhibitor, the etching additive, the metal chelating agent and the hydrogen peroxide stabilizer is (10-20):(0.5-10):(5-30):(0.1-5):(0.01-6).

[0011] When the above three components are combined in a specific mass ratio, the etching rate of the obtained etching solution is faster and the etching rate stability is higher.

[0012] The specific point values ​​in the above (10-20) can be selected as 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc.

[0013] The specific point values ​​in the above (0.5-10) can be selected from 0.5, 0.6, 0.7, 1, 2, 3, 4, 5, 6, 7, 9, 10, etc.

[0014] The specific point values ​​in the above (5-30) can be selected from 5, 8, 10, 13, 15, 20, 23, 27, 28, 29, 30, etc.

[0015] The specific point values ​​(0.1-5) mentioned above can be selected as 0.1, 0.2, 0.4, 0.7, 1, 2, 3, 4, 5, etc.

[0016] The specific point values ​​of the above (0.01-6) can be selected as 0.01, 0.02, 0.04, 0.5, 0.6, 0.7, 1, 2, 3, 4, 5, 6, etc.

[0017] Other specific point values ​​within the above numerical ranges can be selected and will not be described in detail here.

[0018] Preferably, the etching solution composition further comprises water.

[0019] Preferably, the water comprises deionized water.

[0020] Preferably, the deionized water has a specific impedance value greater than 18 MΩ / cm.

[0021] Preferably, the etching inhibitor comprises an organic acid containing one or more carboxyl groups.

[0022] Preferably, the organic acid comprises any one of glycolic acid, acetic acid, butyric acid, formic acid, oxalic acid, propionic acid, malonic acid, tartaric acid, succinic acid, gluconic acid or benzoic acid, or a combination of at least two thereof.

[0023] Preferably, the etching additive contains an inorganic base and / or an inorganic phosphate.

[0024] Preferably, the inorganic base includes any one of potassium hydroxide, sodium hydroxide or sodium carbonate, or a combination of at least two of them.

[0025] Preferably, the inorganic phosphate includes any one or a combination of at least two of tripotassium phosphate, trisodium phosphate, potassium tripolyphosphate, sodium tripolyphosphate or sodium hexametaphosphate.

[0026] Preferably, the molar ratio of the inorganic base to the inorganic phosphate is 1:(1-6).

[0027] The specific point values ​​(1-6) mentioned above can be selected as 1, 2, 3, 4, 5, 6, etc.

[0028] Preferably, the molar ratio of the inorganic phosphate to the hydrogen peroxide stabilizer is 1:(10-15).

[0029] The specific point values ​​(10-15) mentioned above can be selected as 10, 11, 12, 13, 14, 15, etc.

[0030] Preferably, the metal chelating agent includes a compound having both an amino group and a carboxyl group.

[0031] Preferably, the compound having both amino and carboxyl groups includes any one or a combination of at least two of iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminotrimethylenephosphonic acid, hydroxyethylidenediphosphonic acid, iminodisuccinic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, alanine, glutamic acid, aminobutyric acid or glycine.

[0032] Preferably, the hydrogen peroxide stabilizer comprises any one of organic phosphonic acid, dihydroxy alcohols or amines, or a combination of at least two thereof.

[0033] Preferably, the organic phosphonic acid comprises ethylenediaminetetramethylenephosphonic acid.

[0034] Preferably, the dihydroxy alcohols include diethanolamine.

[0035] Preferably, the amine comprises polyacrylamide.

[0036] In a second aspect, the present invention provides a method for preparing the etching solution composition according to the first aspect, the preparation method comprising:

[0037] The etching solution composition is obtained by mixing hydrogen peroxide, an etching inhibitor, an etching additive, a metal chelating agent and a hydrogen peroxide stabilizer.

[0038] In a third aspect, the present invention provides use of the etching solution composition according to the first aspect in metal etching.

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] The etching liquid composition designed by the present invention, which contains three components: an etching inhibitor, an etching additive, and a metal chelating agent, has a fast etching rate and good etching rate stability, excellent stability and safety, and a long service life. In addition, the etching inhibitor, the etching additive, and the metal chelating agent have a certain synergistic effect in increasing the etching rate. DETAILED DESCRIPTION

[0041] To further illustrate the technical means and effects of the present invention, the present invention is further described below with reference to the embodiments and drawings. It should be understood that the specific embodiments described herein are only used to explain the present invention, rather than to limit the present invention.

[0042] If no specific techniques or conditions are specified in the examples, the experiments were carried out according to the techniques or conditions described in the literature in the field or according to the product instructions. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased through regular channels.

[0043] Example 1

[0044] This embodiment provides an etching solution composition, which includes the following components in parts by mass: 15 parts of hydrogen peroxide, 5 parts of an etching inhibitor (malonic acid), 7 parts of an etching additive (potassium hydroxide), 8 parts of an etching additive (potassium tripolyphosphate), 2.5 parts of a metal chelating agent (diethylenetriaminepentaacetic acid), and 3 parts of a hydrogen peroxide stabilizer (diethanolamine).

[0045] The preparation method comprises the following steps: mixing hydrogen peroxide, an etching inhibitor, an etching additive, a metal chelating agent and a hydrogen peroxide stabilizer to obtain the product.

[0046] Example 2

[0047] This embodiment provides an etching solution composition comprising the following components, by weight: 10 parts hydrogen peroxide, 0.5 parts etching inhibitor (succinic acid), 2 parts etching additive (sodium hydroxide), 3 parts etching additive (trisodium phosphate), 0.1 parts metal chelating agent (aminotrimethylenephosphonic acid), and 0.01 parts hydrogen peroxide stabilizer (ethylenediaminetetramethylenephosphonic acid). The preparation method is similar to that of Example 1.

[0048] Example 3

[0049] This embodiment provides an etching solution composition comprising the following components, by weight: 20 parts hydrogen peroxide, 10 parts etching inhibitor (glycolic acid), 10 parts etching additive (sodium carbonate), 20 parts etching additive (sodium tripolyphosphate), 5 parts metal chelating agent (alanine), and 6 parts hydrogen peroxide stabilizer (polyacrylamide). The preparation method is similar to that of Example 1.

[0050] Example 4

[0051] This embodiment provides an etching solution composition comprising the following components, by weight: 13 parts hydrogen peroxide, 3 parts etching inhibitor (acetic acid), 5 parts etching additive (potassium hydroxide), 8 parts etching additive (tripotassium phosphate), 0.5 parts metal chelating agent (glycine), 0.5 parts hydrogen peroxide stabilizer (diethanolamine), and 0.5 parts hydrogen peroxide stabilizer (ethylenediaminetetramethylenephosphonic acid). The preparation method is similar to that of Example 1.

[0052] Example 5

[0053] The present embodiment provides an etching solution composition comprising the following components, by mass: 17 parts hydrogen peroxide, 7 parts etching inhibitor (tartaric acid), 7 parts etching additive (potassium hydroxide), 10 parts etching additive (trisodium phosphate), 4 parts metal chelating agent (hydroxyethylidene diphosphonic acid), 4 parts hydrogen peroxide stabilizer (diethanolamine), and 1 part hydrogen peroxide stabilizer (polyacrylamide). The preparation method is similar to that of Example 1.

[0054] Example 6

[0055] The present embodiment provides an etching solution composition comprising the following components, by mass: 20 parts hydrogen peroxide, 1 part etching inhibitor (gluconic acid), 3 parts etching additive (sodium hydroxide), 2 parts etching additive (sodium hexametaphosphate), 1 part metal chelating agent (aminobutyric acid), and 1 part hydrogen peroxide stabilizer (diethanolamine). The preparation method is similar to that of Example 1.

[0056] Example 7

[0057] This embodiment provides an etching solution composition comprising the following components, by weight: 20 parts hydrogen peroxide, 9 parts etching inhibitor (oxalic acid), 28 parts etching additive (potassium hydroxide), 4 parts metal chelating agent (glutamic acid), and 5 parts hydrogen peroxide stabilizer (diethanolamine). The preparation method is similar to that of Example 1.

[0058] Example 8

[0059] This embodiment provides an etching solution composition comprising the following components, by mass: 20 parts hydrogen peroxide, 6 parts etching inhibitor (propionic acid), 20 parts etching additive (potassium tripolyphosphate), 3 parts metal chelating agent (iminodisuccinic acid), 3 parts hydrogen peroxide stabilizer (ethylenediaminetetramethylenephosphonic acid), and 1 part hydrogen peroxide stabilizer (polyacrylamide). The preparation method is similar to that of Example 1.

[0060] Comparative Example 1

[0061] This comparative example provides an etching solution composition that differs from Example 1 only in that it does not contain an etching inhibitor (malonic acid). Instead, its mass fraction is proportionally distributed to the mass fractions of the etching additives (potassium hydroxide and potassium tripolyphosphate) and the metal chelating agent (diethylenetriaminepentaacetic acid). The preparation method is similar to that of Example 1.

[0062] Comparative Example 2

[0063] This comparative example provides an etching solution composition that differs from Example 1 only in that it does not contain the etching additives (potassium hydroxide and potassium pyrophosphate), and instead proportions thereof to the etching inhibitor (malonic acid) and metal chelator (diethylenetriaminepentaacetic acid). The preparation method is similar to that of Example 1.

[0064] Comparative Example 3

[0065] This comparative example provides an etching solution composition that differs from Example 1 only in that it does not contain a metal chelating agent (diethylenetriaminepentaacetic acid), and instead distributes its mass proportions proportionally to the mass of the etching inhibitor (malonic acid) and etching additives (potassium hydroxide and potassium pyrophosphate). The preparation method is similar to that of Example 1.

[0066] Comparative Example 4

[0067] This comparative example provides an etching solution composition that differs from Example 1 only in that it does not contain the etching inhibitor (malonic acid) and etching additives (potassium hydroxide and potassium pyrophosphate), and instead proportions thereof to the metal chelating agent (diethylenetriaminepentaacetic acid). The preparation method is similar to that of Example 1.

[0068] Comparative Example 5

[0069] This comparative example provides an etching solution composition that differs from Example 1 only in that it does not contain an etching inhibitor (malonic acid) and a metal chelator (diethylenetriaminepentaacetic acid), and instead proportions thereof to the etching additives (potassium hydroxide and potassium pyrophosphate). The preparation method is similar to that of Example 1.

[0070] Comparative Example 6

[0071] This comparative example provides an etching solution composition that differs from Example 1 only in that it does not contain the etching additives (potassium hydroxide and potassium pyrophosphate) and the metal chelating agent (diethylenetriaminepentaacetic acid), and instead proportions thereof by weight to the etching inhibitor (malonic acid). The preparation method is similar to that of Example 1.

[0072] Test Case

[0073] The test method is: the size of the present invention is 8 inches and the thickness is For a titanium layer wafer, the thickness of the titanium layer is marked at 32 points on the wafer, and the average of the 32 points is obtained. The etching time is 60s, and the etching solution temperature is controlled at 30°C. The etching rate = average thickness of the etched titanium layer / etching time (unit: ). According to the above method, the rate of the test solution at 0h, 24h, 48h, 72h and 96h was measured respectively, and the rate when the titanium content in the solution was 500ppm at 0h was then calculated. The percentage decrease in the rate when the titanium content was 500ppm at 48h, 96h and 0h was calculated respectively. If the percentage decrease in the rate when the titanium content was 500ppm at 48h, 96h and 0h was less than 2%, 5% and 5% respectively, the result was excellent. The test results are shown in Table 1.

[0074] Table 1

[0075]

[0076]

[0077] The results show that the etching rate of the etching solutions of Examples 1-8 can reach a maximum of The percentage of rate reduction at 48h, 96h and 0h with a titanium content of 500ppm can be as low as 0.6%, 1.1% and 1.1%, respectively, indicating that the etching rate of the etching solution composition of the present invention is fast and the etching rate stability is good; Comparative Examples 1-3 lack one of the etching inhibitor, etching additive and metal chelating agent compared with Example 1, and the rate at 96h is only The percentage of rate decrease of titanium content 500ppm at 48h, 96h and 0h is higher than 2%, 5% and 5%, respectively, which is a poor result. Comparative Examples 4-6 lack two components of etching inhibitor, etching additive and metal chelating agent compared with Example 1, and the rate at 96h is only The percentage decrease in the rate of 500 ppm of titanium content at 48h, 96h and 0h is as high as 20.3%, 47.3% and 24.3%, respectively, which are poor results. This shows that the etching solution composition containing the three components of the etching inhibitor, the etching additive and the metal chelating agent designed by the present invention has a fast etching rate and good etching rate stability, excellent stability and safety, and a long service life. In addition, the etching inhibitor, the etching additive and the metal chelating agent have a certain synergistic effect in increasing the etching rate.

[0078] In summary, the etching solution composition containing the three components of the etching inhibitor, the etching additive and the metal chelating agent designed in the present invention has a fast etching rate and good etching rate stability, excellent stability and safety, and a long service life. In addition, the etching inhibitor, the etching additive and the metal chelating agent have a certain synergistic effect in increasing the etching rate.

[0079] The applicant states that the present invention is intended to illustrate the detailed methods of the present invention through the above-described embodiments, but the present invention is not limited to the above-described detailed methods, that is, it does not mean that the present invention must rely on the above-described detailed methods in order to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions for various raw materials in the products of the present invention, addition of auxiliary ingredients, and selection of specific methods, etc., are all within the scope of protection and disclosure of the present invention.

Claims

1. An etching solution composition, characterized in that The etching solution composition includes hydrogen peroxide, an etching inhibitor, an etching additive, a metal chelating agent, and a hydrogen peroxide stabilizer in a mass ratio of (14-16):(4-6):(13-20):(2-2.5):(2-3); The etching inhibitor is an organic acid containing one or more carboxyl groups; the etching additive contains an inorganic base and an inorganic phosphate; the inorganic phosphate is any one of potassium pyrophosphate, sodium tripolyphosphate or sodium hexametaphosphate, or a combination of at least two thereof; The molar ratio of the inorganic base to the inorganic phosphate is 1:(1-6).

2. The etching solution composition according to claim 1, wherein The etching solution composition also includes water.

3. The etching solution composition according to claim 2, characterized in that The water includes deionized water.

4. The etching solution composition according to claim 3, characterized in that The deionized water has a specific impedance value greater than 18 MΩ / cm.

5. The etching solution composition according to claim 1, wherein The organic acid includes any one of glycolic acid, acetic acid, butyric acid, formic acid, oxalic acid, propionic acid, malonic acid, tartaric acid, succinic acid, gluconic acid or benzoic acid, or a combination of at least two thereof.

6. The etching solution composition according to claim 1, characterized in that The inorganic base includes any one of potassium hydroxide, sodium hydroxide or sodium carbonate, or a combination of at least two of them.

7. The etching solution composition according to claim 1, characterized in that The molar ratio of the inorganic phosphate to the hydrogen peroxide stabilizer is 1:(10-15).

8. The etching solution composition according to claim 1, wherein The metal chelating agent includes a compound having both an amino group and a carboxyl group.

9. The etching solution composition according to claim 8, characterized in that The compound having both an amino group and a carboxyl group includes any one of iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminotrimethylenephosphonic acid, hydroxyethylidenediphosphonic acid, iminodisuccinic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, alanine, glutamic acid, aminobutyric acid or glycine, or a combination of at least two thereof.

10. The etching solution composition according to claim 1, characterized in that The hydrogen peroxide stabilizer includes any one of organic phosphonic acid, dihydroxy alcohols or amines, or a combination of at least two of them.

11. The etching solution composition according to claim 10, characterized in that The organic phosphonic acid includes ethylenediaminetetramethylenephosphonic acid.

12. The etching solution composition according to claim 10, characterized in that The dihydroxy alcohols include diethanolamine.

13. The etching solution composition according to claim 10, characterized in that The amines include polyacrylamides.

14. A method for preparing the etching solution composition according to any one of claims 1 to 13, characterized in that: The preparation method comprises: The etching solution composition is obtained by mixing hydrogen peroxide, an etching inhibitor, an etching additive, a metal chelating agent, and a hydrogen peroxide stabilizer in a mass ratio of (14-16):(4-6):(13-20):(2-2.5):(2-3); The etching inhibitor is an organic acid containing one or more carboxyl groups; the etching additive contains an inorganic base and an inorganic phosphate; the inorganic phosphate is any one of potassium pyrophosphate, sodium tripolyphosphate or sodium hexametaphosphate, or a combination of at least two thereof; and the molar ratio of the inorganic base to the inorganic phosphate is 1:(1-6).

15. Use of the etching solution composition according to any one of claims 1 to 13 in metal etching.

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