Etching solution for TiAlTi substrates with different thicknesses as well as preparation method and application of etching solution

Abstract

The invention relates to an etching solution for TiAlTi substrates with different thicknesses as well as a preparation method and application of the etching solution. The etching liquid for the TiAlTi substrates with different thicknesses comprises the following components in parts by weight: 10-20 parts of organic acid; 40-50 parts of inorganic acid; 10-20 parts of an organic solvent; 0.5-1 part of an additive; and 10-25 parts of ultrapure water. According to the invention, 1-(3-((4-(2-fluorophenyl) piperazine-1-yl) methyl)-4-methoxyphenyl)-2, 3, 4, 9-tetrahydro-1H-pyridino [3, 4-B] indole-3-carboxylic acid is combined with another organic acid, and the 1-(3-((4-(2-fluorophenyl) piperazine-1-yl) methyl)-4-methoxyphenyl)-2, 3, 4, 9-tetrahydro-1H-pyridino [3, 4-B] indole-3-carboxylic acid is used as a catalyst for preparing the 2, 3, 4, 9-tetrahydro-1H-pyridino [3, 4-B] indole-3-carboxylic acid derivative. F ions provided by one kind of organic acid and 1-(3-((4-(2-fluorophenyl) piperazin-1-yl) methyl)-4-methoxyphenyl)-2, 3, 4, 9-tetrahydro-1H-pyrido [3, 4-B] indole-3-carboxylic acid can be used for etching titanium, and benzene rings contained in the other kind of organic acid and 1-(3-((4-(2-fluorophenyl) piperazin-1-yl) methyl)-4-methoxyphenyl)-2, 3, 4, 9-tetrahydro-1H-pyrido [3, 4-B] indole-3-carboxylic acid can be adsorbed on a metal surface to uniformly etch a metal layer.

Description

Technical Field

[0001] The invention belongs to the field of etching liquid, and in particular relates to an etching liquid for TiAlTi substrates of different thicknesses and a preparation method and application thereof. Background Art

[0002] In recent years, Micro-LED has become a research hotspot in the display field and has attracted widespread attention worldwide. Recently, a monolithic Micro-LED micro-display technology has been developed, which bonds the micron-scale Si-based Micro-LED array to the wafer of the high-efficiency CMOS driving backplane through an inverted structure to achieve wafer-level optoelectronic heterogeneous integration. The full-colorization of monolithic Micro-LED micro-displays has yet to be solved, but blue or green monochrome monolithic micro-display array chips have been developed. This monochrome monolithic Micro-LED micro-display chip has broad application prospects. In the manufacturing process of monochrome monolithic Micro-LED micro-display chips, Ti / Al / Ti multi-layer metal layers are usually deposited on the substrate.

[0003] Etching is an important step in the production process of monochrome monolithic Micro-LED micro-display chips. However, the chemical properties of metal titanium and aluminum are quite different, resulting in mismatched etching speeds of titanium and aluminum films of different thicknesses in the etching solution. In order to meet the needs of subsequent processes, when wet etching the titanium, aluminum and titanium three layers, the Ti layer should not protrude from the top and bottom after etching, and the critical dimension loss of the metal should be appropriate.

[0004] Therefore, it is necessary to develop an etching solution that can be used for etching titanium-aluminum-titanium three-layer metals of different thicknesses, and to ensure that there is no protrusion of the Ti layer after etching and the critical size loss of the metal is small. Summary of the invention

[0005] The technical problem solved by the present invention is: when wet etching titanium, aluminum and titanium three-layer metal, the top and bottom Ti layers bulge out after etching, and the critical size loss of the metal is not moderate.

[0006] In view of the technical problems existing in the prior art, the present invention designs an etching solution and a preparation method for TiAlTi substrates of different thicknesses, which can reduce or even avoid the occurrence of protrusions of the top and bottom Ti layers and ensure that the critical size loss of the metal after etching is moderate.

[0007] It should be noted that, in the present invention, unless otherwise specified, the specific meaning of "including" in relation to composition limitations and descriptions includes both open-ended "including", "comprising" and similar meanings, as well as closed-ended "consisting of..." and similar meanings.

[0008] In order to solve the above-mentioned technical problems, the present invention adopts the following solutions:

[0009] An etching solution for TiAlTi substrates of different thicknesses, characterized in that it comprises the following components calculated by weight:

[0010] 10-20 parts of organic acid;

[0011] 40-50 parts of inorganic acid;

[0012] 10-20 parts of organic solvent;

[0013] Additives 0.5-1 part;

[0014] 10-25 parts of ultrapure water.

[0015] Furthermore, the organic acid includes 1-(3-((4-(2-fluorophenyl)piperazin-1-yl)methyl)-4-methoxyphenyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-B]indole-3-carboxylic acid (CAS No.: 874374-25-1).

[0016] Furthermore, the organic acid also includes at least one of aristolochic acid, tartaric acid, oxalic acid, acetic acid, citric acid, sebacic acid, lactic acid, glycine and malic acid.

[0017] Furthermore, the organic acid is preferably 12-20 parts.

[0018] Furthermore, the inorganic acid is any one or more of nitric acid, hydrochloric acid, phosphoric acid, hydrofluoric acid, and hydrobromic acid.

[0019] Furthermore, the inorganic acid is preferably 42-50 parts.

[0020] Furthermore, the organic solvent is any one or more of dimethyl sulfoxide, diethyl sulfoxide, and ethyl methyl sulfoxide.

[0021] Furthermore, the organic solvent is preferably 10-18 parts.

[0022] Furthermore, the additive is any one or more of L-octahydroindole-2-carboxylic acid (CAS No.: 80875-98-5), (S)-(+)-binaphthol di-p-toluenesulfonate, R-1,1′-binaphthol, and (S,S)-(+)-N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine.

[0023] Furthermore, the additive is preferably 0.6-1 part.

[0024] Furthermore, the ultrapure water is deionized water with a resistance of at least 18M.

[0025] The present invention also provides a method for preparing the etching solution for TiAlTi substrates of different thicknesses, which is characterized by comprising the following steps:

[0026] Step 1: Add the organic acid into the organic solvent and stir evenly, then add the additive and continue stirring;

[0027] Step 2: Add inorganic acid into ultrapure water and stir evenly;

[0028] Step 3: Add the solution prepared in step 1 to the solution prepared in step 2 and stir evenly to obtain an etching solution.

[0029] Furthermore, in step 1, 1-(3-((4-(2-fluorophenyl)piperazin-1-yl)methyl)-4-methoxyphenyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-B]indole-3-carboxylic acid and aristolochic acid are mixed evenly, added to an organic solvent and stirred evenly, and then an additive is added and stirred continuously.

[0030] Furthermore, the stirring time after adding the organic solvent in step 1 is 10-30 minutes; and the additive is added and stirring is continued for 10-30 minutes.

[0031] Furthermore, the mixing and stirring time in step 2 is 5-10 minutes.

[0032] Furthermore, the mixing and stirring time in step 3 is 10-30 min.

[0033] The present invention also provides an etching method for the etching solution of TiAlTi substrates of different thicknesses, characterized by comprising the following steps:

[0034] The Ti / Al / Ti substrate is placed in the etching solution for TiAlTi substrates of different thicknesses for etching. After the etching is completed, the Ti / Al / Ti substrate is rinsed and dried to obtain an etched substrate.

[0035] Furthermore, the temperature of the etching solution is 20°C-40°C.

[0036] Furthermore, the etching time is 50-150s.

[0037] The present invention also provides a use of the etching solution for TiAlTi substrates with different thicknesses in the preparation of Ti / Al / Ti substrates.

[0038] In the present invention, the organic acid is preferably component A and component B, wherein component A is 1-(3-((4-(2-fluorophenyl)piperazine-1-yl)methyl)-4-methoxyphenyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-B]indole-3-carboxylic acid; and component B is at least one of aristolochic acid, tartaric acid, oxalic acid, acetic acid, citric acid, sebacic acid, lactic acid, glycine and malic acid. Component B is preferably aristolochic acid.

[0039] In the present invention, the mass ratio of component A to component B is (0.5-2):1.

[0040] In the present invention, the mass ratio of component A to component B is 1.5:1.

[0041] In the present invention, the mass ratio of 1-(3-((4-(2-fluorophenyl)piperazin-1-yl)methyl)-4-methoxyphenyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-B]indole-3-carboxylic acid to aristolochic acid is (0.5-2):1.

[0042] In the present invention, the mass ratio of 1-(3-((4-(2-fluorophenyl)piperazin-1-yl)methyl)-4-methoxyphenyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-B]indole-3-carboxylic acid to aristolochic acid is preferably 1.5:1.

[0043] In the present invention, the inorganic acid is preferably hydrochloric acid.

[0044] In the present invention, the organic solvent is preferably dimethyl sulfoxide.

[0045] In the present invention, the additive is preferably L-octahydroindole-2-carboxylic acid.

[0046] In the etching method of the etching solution for TiAlTi substrates of different thicknesses of the present invention, the etching time is preferably 80-110 s.

[0047] In the etching method of the etching solution for TiAlTi substrates of different thicknesses of the present invention, in step 1, component A and component B are mixed evenly, added into an organic solvent and stirred evenly, and then an additive is added and stirred continuously.

[0048] The present invention provides an etching solution for TiAlTi substrates of different thicknesses and a preparation method and application thereof, which have the following beneficial effects:

[0049] 1. The present invention adopts a combination of 1-(3-((4-(2-fluorophenyl)piperazine-1-yl)methyl)-4-methoxyphenyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-B]indole-3-carboxylic acid and another organic acid. The F ions provided by 1-(3-((4-(2-fluorophenyl)piperazine-1-yl)methyl)-4-methoxyphenyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-B]indole-3-carboxylic acid can etch titanium, and the benzene ring contained in another organic acid and 1-(3-((4-(2-fluorophenyl)piperazine-1-yl)methyl)-4-methoxyphenyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-B]indole-3-carboxylic acid can be adsorbed on the surface of titanium metal, thereby ensuring the morphology after etching without top protrusion.

[0050] 2. The present invention adopts two organic acids and an amino group in L-octahydroindole-2-carboxylic acid to electrophilically combine, and L-octahydroindole-2-carboxylic acid is a chiral catalyst, which can make 1-(3-((4-(2-fluorophenyl)piperazine-1-yl)methyl)-4-methoxyphenyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-B]indole-3-carboxylic acid and aristolochic acid form a chiral molecule, which can maintain a stable metal etching rate. When etching a Ti / Al / Ti substrate, the top and bottom Ti layers can be prevented from protruding, and the ratio of the two can be adjusted for Ti / Al / Ti substrates of different thicknesses (such as Ti / Al / Ti) is etched. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 : After etching using the etching solution of Example 1 Side etching effect of Ti / Al / Ti substrate, magnified 40,000 times;

[0052] Figure 2 : After etching with the etching solution of Comparative Example 2 Side etching effect of Ti / Al / Ti substrate, magnified 40,000 times;

[0053] Figure 3 : After etching using the etching solution of Example 1 Side etching effect of Ti / Al / Ti substrate, magnified 40,000 times;

[0054] Figure 4 : After etching with the etching solution of Comparative Example 2 Side etching effect of Ti / Al / Ti substrate, magnified 40,000 times;

[0055] Figure 5 : After etching with the etching solution of Example 1 Top view of Ti / Al / Ti substrate, magnified 20,000 times;

[0056] Figure 6 : After etching with the etching solution of Comparative Example 2 Aerial view of the Ti / Al / Ti substrate, magnified 20,000 times. DETAILED DESCRIPTION

[0057] The present invention will be further described below in conjunction with specific embodiments and accompanying drawings:

[0058] The etching solutions for TiAlTi substrates of different thicknesses involved in Examples 1-9 and Comparative Examples 1-3 of the present invention include components and mass ratios as shown in Tables 1 and 2.

[0059] Table 1 Examples 1-9

[0060]

[0061]

[0062] Table 2 Comparative Examples 1-3

[0063]

[0064]

[0065] Table 3 Test data

[0066] CD-loss(μm) Morphology after etching Example 1 0.65 No Ti protrusion Example 2 1.64 No Ti protrusion Example 3 1.12 No Ti protrusion Example 4 0.95 No Ti protrusion Example 5 0.84 No Ti protrusion Example 6 1.07 No Ti protrusion Example 7 0.83 No Ti protrusion Example 8 1.42 No Ti protrusion Example 9 0.97 No Ti protrusion Comparative Example 1 3.01 Ti layer cannot be etched Comparative Example 2 2.98 Top Ti layer protrudes Comparative Example 3 2.75 Top Ti layer protrudes

[0067] Regarding the preparation method of the etching solution for TiAlTi substrates of different thicknesses of the present invention:

[0068] The present invention relates to a plurality of methods for preparing etching solutions in the embodiments and comparative examples, all of which are prepared by referring to the following method:

[0069] Step 1: Add 1-(3-((4-(2-fluorophenyl)piperazin-1-yl)methyl)-4-methoxyphenyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-B]indole-3-carboxylic acid and another organic acid to an organic solvent at room temperature and stir for 30 minutes, then add an additive and stir for 20 minutes;

[0070] Step 2: Add inorganic acid into ultrapure water and stir for 10 minutes;

[0071] Step 3: Add the solution prepared in step 1 to the solution prepared in step 2 and stir for 30 minutes.

[0072] Regarding the etching method of the etching solution for TiAlTi substrates of different thicknesses of the present invention:

[0073] Step 1: Immerse the Ti / Al / Ti substrate in an etching solution for etching; the etching time is 100 s and the etching temperature is 25°C.

[0074] Step 2: Rinse the Ti / Al / Ti substrate in ultrapure water at least twice and blow dry with nitrogen.

[0075] About performance testing and description:

[0076] The test method for performance 1CD-loss is:

[0077] The Ti / Al / Ti sample was etched using the etching solution of the above embodiment and comparative example of the present invention, and then cleaned after etching. The specific steps are as follows:

[0078] Step 1: Place the substrate ( ) was immersed in the etching solution, the etching time was 100s, and the etching temperature was 25℃.

[0079] Step 2: Rinse the Ti / Al / Ti sample in ultrapure water for at least two times and blow dry with nitrogen.

[0080] Step 3: Observe the sample morphology and measure CD-loss under SEM after FIB ion beam cutting. The test results are shown in Figure 5-6 general The CD-loss of the substrate is recorded in Table 3.

[0081] The ultrapure water used in the above steps is deionized water with a resistance of at least 18M.

[0082] The test method for the morphology after performance 2Ti / Al / Ti etching is:

[0083] The Ti / Al / Ti sample was etched using the etching solution of the above embodiment and comparative example of the present invention, and then cleaned after etching. The specific steps are as follows:

[0084] Step 1: Immerse the Ti / Al / Ti substrate in an etching solution for etching; the etching time is 100 s and the etching temperature is 25°C.

[0085] Step 2: Rinse the Ti / Al / Ti substrate in ultrapure water at least twice and blow dry with nitrogen.

[0086] Step 3: Observe the sample morphology under SEM. Figure 1-4 and Table 3.

[0087] The ultrapure water used in the above steps is deionized water with a resistance of at least 18M.

[0088] Analysis of the test results:

[0089] Based on Table 3, it can be seen that after etching with the etching solution of the embodiment of the present invention, there is no protrusion of the Ti layer at the top and the bottom, and the bilateral CD-loss is less than 2μm, while Comparative Example 1 lacks 1-(3-((4-(2-fluorophenyl)piperazine-1-yl)methyl)-4-methoxyphenyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-B]indole-3-carboxylic acid, resulting in the inability to etch the Ti layer; Comparative Example 2 lacks additives, resulting in a protrusion of the top Ti layer. Comparative Example 3 lacks another organic acid, aristolochic acid, resulting in a protrusion of the top Ti layer.

[0090] Further comparison and explanation through the attached drawings in the specification :

[0091] Figure 1 After etching using the etching solution of Example 1 Side etching effect of Ti / Al / Ti substrate, magnified 40,000 times;

[0092] Figure 2 After etching with the etching solution of Comparative Example 2 Side etching effect of Ti / Al / Ti substrate, magnified 40,000 times;

[0093] Figure 3 After etching using the etching solution of Example 1 Side etching effect of Ti / Al / Ti substrate, magnified 40,000 times;

[0094] Figure 4 After etching with the etching solution of Comparative Example 2 Side etching effect of Ti / Al / Ti substrate, magnified 40,000 times;

[0095] Figure 5 After etching using the etching solution of Example 1 Top view of Ti / Al / Ti substrate, magnified 20,000 times;

[0096] Figure 6 After etching with the etching solution of Comparative Example 2 Aerial view of the Ti / Al / Ti substrate, magnified 20,000 times.

[0097] pass Figure 1-6 By comparison, it can be proved that after etching with the etching solution in Comparative Example 2, the top Ti layer is obviously protruded, and the CD-loss is greater than that in Example 1.

[0098] pass Figure 1-4 By comparison, it can be seen that the etching solution of Example 1 has a good The substrates all have good etching effects, and there is no protrusion of the top and bottom Ti layers after etching.

[0099] pass Figure 5 and Figure 6 By comparison, it can be seen that when etching substrates of the same thickness, the CD-loss after etching by the etching solution of Example 1 is smaller.

[0100] The etching solution of the present invention adopts 1-(3-((4-(2-fluorophenyl)piperazine-1-yl)methyl)-4-methoxyphenyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-B]indole-3-carboxylic acid and another organic acid combination. The F ions provided by the 1-(3-((4-(2-fluorophenyl)piperazine-1-yl)methyl)-4-methoxyphenyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-B]indole-3-carboxylic acid can be used to etch titanium. The organic acid and the benzene ring contained in the 1-(3-((4-(2-fluorophenyl)piperazine-1-yl)methyl)-4-methoxyphenyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-B]indole-3-carboxylic acid can be adsorbed on the surface of titanium metal, thereby ensuring the morphology after etching without titanium protrusion.

[0101] The present invention is described exemplarily above in conjunction with the embodiments and drawings. It is obvious that the implementation of the present invention is not limited to the above-mentioned methods. As long as various improvements are made using the method concept and technical solution of the present invention, or the concept and technical solution of the present invention are directly applied to other occasions without improvement, they are all within the protection scope of the present invention.

Claims

1. An etching solution for TiAlTi substrates of different thicknesses, characterized in that: Calculated by weight, it includes the following components: 10-20 parts of organic acid; 40-50 parts of inorganic acid; 10-20 parts of organic solvent; Additives 0.5-1 part; 10-25 parts of ultrapure water.

2. The etching solution for TiAlTi substrates of different thicknesses according to claim 1, characterized in that: The organic acid includes 1-(3-((4-(2-fluorophenyl)piperazin-1-yl)methyl)-4-methoxyphenyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-B]indole-3-carboxylic acid.

3. The etching solution for TiAlTi substrates of different thicknesses according to claim 2, characterized in that: The organic acid also includes at least one of aristolochic acid, tartaric acid, oxalic acid, acetic acid, citric acid, sebacic acid, lactic acid, glycine and malic acid.

4. The etching solution for TiAlTi substrates of different thicknesses according to claim 3, characterized in that: The mass ratio of 1-(3-((4-(2-fluorophenyl)piperazine-1-yl)methyl)-4-methoxyphenyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-B]indole-3-carboxylic acid and aristolochic acid in the organic acid is (0.5-2):

1.

5. The etching solution for TiAlTi substrates of different thicknesses according to claim 1, characterized in that: The inorganic acid is any one or more of nitric acid, hydrochloric acid, phosphoric acid, hydrofluoric acid and hydrobromic acid.

6. The etching solution for TiAlTi substrates of different thicknesses according to claim 1, characterized in that: The organic solvent is any one or more of dimethyl sulfoxide, diethyl sulfoxide and ethyl methyl sulfoxide.

7. The etching solution for TiAlTi substrates of different thicknesses according to claim 1, characterized in that: The additive is any one or more of L-octahydroindole-2-carboxylic acid, (S)-(+)-binaphthol di-p-toluenesulfonate, R-1,1′-binaphthol, and (S,S)-(+)-N,N′-bis(3,5-di-tert-butyl salicylidene)-1,2-cyclohexanediamine.

8. A method for preparing an etching solution for TiAlTi substrates of different thicknesses according to any one of claims 1 to 7, characterized in that The following steps are involved: Step 1: Add the organic acid into the organic solvent and stir evenly, then add the additive and continue stirring; Step 2: Add inorganic acid into ultrapure water and stir evenly; Step 3: Add the solution prepared in step 1 to the solution prepared in step 2 and stir evenly to obtain an etching solution.

9. An etching method for TiAlTi substrates of different thicknesses using an etching solution as claimed in any one of claims 1 to 7, characterized in that The following steps are involved: The Ti / Al / Ti substrate is placed in the etching solution for TiAlTi substrates of different thicknesses for etching. After the etching is completed, the Ti / Al / Ti substrate is rinsed and dried to obtain an etched substrate.

10. Use of the etching solution for TiAlTi substrates of different thicknesses according to any one of claims 1 to 7 in the preparation of Ti / Al / Ti substrates.

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