Cu / Mo and Cu / MTD compatible etching solution and application thereof

Abstract

The invention provides an etching solution compatible with Cu / Mo and Cu / MTD and application of the etching solution. The etching solution comprises a main agent and an auxiliary agent, the main agent comprises the following components in parts by weight: 5-22 parts of an oxidizing agent, 1-15 parts of organic acid, 0.01-5 parts of inorganic acid, 0.5-15 parts of organic alkali, 0.01-5 parts of a stabilizer, 0.01-1 part of a metal inhibitor and 1-100 parts of water. The etching solution provided by the invention can be effectively compatible with two different metal structures, namely Cu / Mo and Cu / MTD, and can realize a good etching effect on different metal film layers in the etching process, so that the problem of poor etching caused by poor compatibility of the etching solution is reduced, and the yield of products is improved; the etching solution has excellent etching performance on Cu / Mo and Cu / MTD alloy double-layer films and the like, no residue is left after etching, substrate materials such as a glass substrate and the like cannot be damaged, and the high requirement of the modern electronic manufacturing process on the etching solution is met.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of etching solution, and particularly relates to an etching solution compatible with Cu / Mo and Cu / MTD and application thereof. BACKGROUND

[0002] Liquid crystal display devices have many advantages such as lightness, thinness, energy saving, and no radiation, and are widely used. Existing liquid crystal display devices usually include a backlight module, a polarizer, a TFT array substrate, a CF substrate, and liquid crystals arranged between the TFT array substrate and the CF substrate, the rotation direction of the liquid crystals is controlled by supplying power to the TFT array substrate, and the light of the backlight module is projected to the CF substrate to generate a picture.

[0003] At present, in the production process of liquid crystal panels, with the demand for large size, high resolution, and driving frequency of liquid crystal display terminals such as televisions, it is urgent to solve the resistance / capacitance time delay problem in the TFT array substrate. In view of the fact that copper wires have lower resistivity and good anti-electromigration ability compared with aluminum wires, most metal wires in the TFT array process use copper wires.

[0004] For copper wire technology, the etching solution of two-layer metal structure of Cu / Mo, Cu / Ti, Cu / MTD, Cu / MoNb, etc. has been used for mass production in the industry. However, some existing etching solutions cannot well compatible with different metal structures, resulting in poor etching effect, etching residue, damage to the substrate, and other problems. Therefore, it is of great practical significance to develop an etching solution that can effectively compatible with Cu / Mo and Cu / MTD, has stable performance, and low cost.

[0005] CN116180083B discloses an etching solution for liquid crystal panel MTD-Cu-MTD and a preparation method thereof. The etching solution, by mass percentage, includes 1-20% of an oxide, 0.01-5% of an oxide stabilizer, 1-10% of an organic acid, 1-10% of an organic base, 1-5% of an inorganic acid, 0.5-5% of an additive, 0.01-5% of a corrosion inhibitor, and deionized water to make up the balance. The etching solution provided by the application can have a suitable etching rate, avoids the phenomena of protrusion of the top layer metal caused by too slow etching rate and serious side etching of the top layer caused by too fast etching rate of the existing three-layer metal etching solution, and effectively improves the etching quality of the etching solution for three-layer metal.

[0006] CN118685774A discloses a Cu-MTD etching liquid for liquid crystal panel and a preparation method thereof, which comprises the following components in a weight ratio: hydrogen peroxide 5-18%, stabilizer 0.01-1%, organic acid 1-12%, organic base 1-10%, corrosion inhibitor 0.01-2%, and the rest is ultrapure water. The copper etching liquid has the advantages of strong compatibility, stable etching efficiency and good etching effect, and can effectively solve the problems in the prior art.

[0007] CN118085870A discloses an etching liquid, an etching method and a preparation method of an array substrate, provides an etching liquid, which comprises 8-15 parts by mass of an oxidizing agent, 0.0005-0.006 parts by mass of a fluoride, 3-6 parts by mass of a chelating agent, 2-5 parts by mass of an organic base, a azole compound with a mass fraction of less than or equal to 2 parts and an anti-potential etching agent with a mass fraction of less than or equal to 3 parts, and 60-85 parts by mass of a solvent. The metal layer and the semiconductor layer in the array substrate are etched by one wet etching and one dry etching, which successfully improves the amorphous silicon layer etching tailing problem, and reduces the etching liquid consumption, reduces the production cost.

[0008] However, the above methods cannot meet the demand for etching liquid compatible with Cu / Mo and Cu / MTD in the prior art. Therefore, how to provide an etching liquid compatible with Cu / Mo and Cu / MTD with good stability and etching effect has become a problem to be solved. SUMMARY

[0009] In view of the deficiencies of the prior art, the purpose of the present application is to provide an etching liquid compatible with Cu / Mo and Cu / MTD and its application. The etching liquid provided by the present application can effectively compatible with Cu / Mo and Cu / MTD two different metal structures, and can achieve good etching effect on different metal film layers in the etching process, reducing the etching problem caused by poor compatibility of etching liquid, and improving the yield of products; has excellent etching performance on Cu / Mo and Cu / MTD alloy double-layer film, etc., and has no residue after etching, and will not damage the substrate material such as glass substrate, etc., meeting the high requirements of modern electronic manufacturing process on etching liquid.

[0010] To achieve the purpose of the present application, the following technical solutions are adopted:

[0011] On the one hand, the present application provides an etching liquid compatible with Cu / Mo and Cu / MTD, which comprises a main agent and an auxiliary agent;

[0012] The main agent includes oxidizing agent 5-22 parts by weight, organic acid 1-15 parts, inorganic acid 0.01-5 parts, organic base 0.5-15 parts, stabilizer 0.01-5 parts, metal inhibitor 0.01-1 part and water 1-100 parts;

[0013] The number of parts of the oxidizing agent can be 5, 10, 15, 20 or 22, the number of parts of the organic acid can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, etc., the number of parts of the inorganic acid can be 0.01, 0.1, 0.5, 1, 2, 3, 4 or 5, etc., the number of parts of the organic base can be 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, etc., the number of parts of the stabilizer can be 0.01, 0.1, 0.5, 1, 2, 3, 4 or 5, etc., the number of parts of the metal inhibitor can be 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, etc., and the number of parts of the water can be 1, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100, etc., but not limited to the above listed values, other values not listed within the above numerical range are also applicable.

[0014] The auxiliary agent includes organic acid 5-50 parts by weight, inorganic acid 0.01-5 parts, organic base 0.5-30 parts, stabilizer 0.01-5 parts, metal inhibitor 0.01-2 parts and water 1-100 parts.

[0015] The number of parts of the organic acid can be 5, 10, 15, 20, 25, 30, 35, 40, 45 or 50, etc., the number of parts of the inorganic acid can be 0.01, 0.1, 0.5, 1, 2, 3, 4 or 5, etc., the number of parts of the organic base can be 0.5, 1, 5, 10, 15, 20, 25 or 30, etc., the number of parts of the stabilizer can be 0.01, 0.1, 0.5, 1, 2, 3, 4 or 5, etc., the number of parts of the metal inhibitor can be 0.01, 0.1, 0.5, 1, 1.5 or 2, etc., and the number of parts of the water can be 1, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100, etc., but not limited to the above listed values, other values not listed within the above numerical range are also applicable.

[0016] The etching liquid with the specific composition and ratio can effectively compatibly Cu / Mo and Cu / MTD two different metal structures, and can achieve good etching effect on different metal films in the etching process, reduces the etching problem caused by poor compatibility of etching liquid, and improves the yield of products; has excellent etching performance on Cu / Mo and Cu / MTD alloy double-layer film, and has no residue after etching, and will not damage the substrate material such as glass substrate, and meets the high requirements of modern electronic manufacturing process on etching liquid.

[0017] Preferably, the main agent comprises, in parts by weight, 6-20 parts of an oxidizing agent, 1.5-10 parts of an organic acid, 0.01-3 parts of an inorganic acid, 1-10 parts of an organic base, 0.05-1 part of a stabilizer, 0.01-0.05 part of a metal inhibitor, and 1-100 parts of water.

[0018] Preferably, the auxiliary agent comprises, in parts by weight, 10-40 parts of an organic acid, 0.01-3 parts of an inorganic acid, 2-20 parts of an organic base, 0.05-1 part of a stabilizer, 0.01-1.5 parts of a metal inhibitor, and 1-100 parts of water.

[0019] Preferably, the oxidizing agent comprises hydrogen peroxide, and the concentration of hydrogen peroxide in the etching liquid is 8-16%.

[0020] Preferably, the organic acid in the main agent and the auxiliary agent is independently selected from any one or a combination of at least two of acetic acid, malonic acid, succinic acid, malic acid, citric acid, valeric acid, glycine, tartaric acid, salicylic acid, succinic acid, or hydroxyethyl sulfonic acid, preferably a combination of malonic acid, malic acid and citric acid.

[0021] Preferably, the inorganic acid in the main agent and the auxiliary agent is independently selected from any one or a combination of at least two of hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid, preferably phosphoric acid.

[0022] Preferably, the organic base in the main agent and the auxiliary agent is independently selected from any one or a combination of at least two of ethylenediamine, diethylaminopropylamine, propylenediamine, triethanolamine, diethanolamine, dimethyl ethanolamine, isopropanolamine, tris-hydroxymethyl aminomethane, isobutanolamine or triethanolamine, preferably a combination of triethanolamine and isopropanolamine.

[0023] The above specific reagent selection can further improve the effect of the product, improve the compatibility, and make the etching effect of Cu / Mo and Cu / MTD more close.

[0024] Preferably, the stabilizer in the main agent and the auxiliary agent is independently selected from any one or a combination of at least two of phenylurea, p-hydroxybenzenesulfonic acid, glycerol, propylene glycol, ethylene glycol, ethylene glycol monobutyl ether, diethylene glycol or 1,2-propanediol.

[0025] Preferably, the metal inhibitors in the main agent and the auxiliary agent are independently selected from any one or a combination of at least two of 2-sulfanyl furan, pyrrolidine, alloxan, 5-(thiophene-2-yl)-1H-tetrazole, 6-aminopurine, methylpiperazine, hydroxyethylpiperazine, benzotriazole, 3-aminotriazole, 5-aminotetrazole or methyltetrazole.

[0026] Preferably, the main agent and / or the auxiliary agent further comprises a surfactant in a weight fraction of 0.01-10 parts, for example 0.01 parts, 0.1 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, etc., but not limited to the above listed values, and other values not listed in the above range are also applicable.

[0027] Preferably, the surfactants in the main agent and the auxiliary agent are independently selected from any one or a combination of at least two of polyethylene glycol, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, sorbitan fatty acid ester or octadecylamine polyoxyethylene ether.

[0028] In another aspect, the application also provides use of the etching solution compatible with Cu / Mo and Cu / MTD as described above in a Cu / Mo and Cu / MTD etching process.

[0029] Compared with the prior art, the application has the following beneficial effects:

[0030] The application provides an etching solution compatible with Cu / Mo and Cu / MTD, which can effectively compatibly Cu / Mo and Cu / MTD two different metal structures, and can achieve good etching effect on different metal films in the etching process, reduces the etching problem caused by poor compatibility of the etching solution, and improves the yield of products; has excellent etching performance on Cu / Mo and Cu / MTD alloy double-layer films, etc., and has no residue after etching, and will not damage the substrate materials such as glass substrates, and meets the high requirements of modern electronic manufacturing process on the etching solution. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 is the image after Cu-Mo etching in Example 1;

[0032] Figure 2 is the image after Cu-MTD etching in Example 1. DETAILED DESCRIPTION

[0033] The technical solutions of the application are further illustrated by specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the application, and should not be regarded as specific limitations on the application.

[0034] Example 1

[0035] The present embodiment provides an etching solution compatible with Cu / Mo and Cu / MTD, and the raw materials are prepared as follows (in mass percentage) :

[0036] Main agent: oxidizing agent (hydrogen peroxide) 12%, organic acid (malonic acid 3%, malic acid 2%, citric acid 2%) 7%, inorganic acid (phosphoric acid) 0.8%, organic base (isopropanolamine 3%, triethanolamine 5%) 7%, metal inhibitor (benzotriazole) 0.03%, stabilizer (1,2-propanediol) 0.7%, deionized water balance.

[0037] Auxiliary agent: organic acid (salicylic acid 0.1%, malic acid 15%, citric acid 15%) 30.1%, inorganic acid (phosphoric acid) 0.8%, organic base (isopropanolamine) 7%, metal inhibitor (benzotriazole) 0.01%, stabilizer (1,2-propanediol) 0.7%, deionized water balance.

[0038] Mixing each raw material to prepare.

[0039] Example 2

[0040] The present embodiment provides an etching solution compatible with Cu / Mo and Cu / MTD, and the raw materials are prepared as follows (in mass percentage) :

[0041] Main agent: oxidizing agent (hydrogen peroxide) 5%, organic acid (malonic acid 7%, malic acid 4%, citric acid 4%) 15%, inorganic acid (phosphoric acid) 0.01%, organic base (triethanolamine) 15%, metal inhibitor (3-amino triazole) 0.01%, stabilizer (glycerol) 5%, deionized water balance.

[0042] Auxiliary agent: organic acid (malonic acid 3%, malic acid 1%, citric acid 1%) 5%, inorganic acid (phosphoric acid) 5%, organic base (triethanolamine) 30%, metal inhibitor (3-amino triazole) 2%, stabilizer (glycerol) 0.01%, deionized water balance.

[0043] Mixing each raw material to prepare.

[0044] Example 3

[0045] The present embodiment provides an etching solution compatible with Cu / Mo and Cu / MTD, and the raw materials are prepared as follows (in mass percentage) :

[0046] Main agent: oxidizing agent (hydrogen peroxide) 22%, organic acid (malic acid 0.5%, citric acid 0.5%) 1%, inorganic acid (sulfuric acid) 5%, organic base (ethylenediamine) 0.5%, metal inhibitor (benzotriazole) 2%, stabilizer (phenylurea) 0.01%, surfactant (octadecylamine polyoxyethylene ether) 0.1%, deionized water balance.

[0047] Adjuvants: organic acid (malic acid 30%, citric acid 20%) 50%, inorganic acid (sulfuric acid) 0.01%, organic base (ethylenediamine) 0.5%, metal inhibitor (benzotriazole) 0.01%, stabilizer (phenylurea) 5%, surfactant (octadecylamine polyoxyethylene ether) 0.1%, deionized water balance.

[0048] The raw materials were mixed to obtain the product.

[0049] Example 4

[0050] This example provides a Cu / Mo and Cu / MTD compatible etching solution. In the preparation of raw materials, except that no malonic acid is added to the main agent, a portion is distributed to malic acid and citric acid in proportion, and the rest is consistent with Example 1.

[0051] Example 5

[0052] This example provides a Cu / Mo and Cu / MTD compatible etching solution. In the preparation of raw materials, except that no malic acid is added to the main agent, a portion is distributed to malonic acid and citric acid in proportion, and the rest is consistent with Example 1.

[0053] Example 6

[0054] This example provides a Cu / Mo and Cu / MTD compatible etching solution. In the preparation of raw materials, except that no citric acid is added to the main agent, a portion is distributed to malic acid and malonic acid in proportion, and the rest is consistent with Example 1.

[0055] Example 7

[0056] This example provides a Cu / Mo and Cu / MTD compatible etching solution. In the preparation of raw materials, except that phosphoric acid is replaced with an equal amount of sulfuric acid in the main agent, and the rest is consistent with Example 1.

[0057] Example 8

[0058] This example provides a Cu / Mo and Cu / MTD compatible etching solution. In the preparation of raw materials, except that no triethanolamine is added to the main agent, a portion is distributed to isopropanolamine, and the rest is consistent with Example 1.

[0059] Example 9

[0060] This example provides a Cu / Mo and Cu / MTD compatible etching solution. In the preparation of raw materials, except that no isopropanolamine is added to the main agent, a portion is distributed to triethanolamine, and the rest is consistent with Example 1.

[0061] Comparative Example 1

[0062] The embodiment provides an etching solution compatible with Cu / Mo and Cu / MTD, and the preparation raw materials are consistent with those in the embodiment 1 except that triethanolamine and isopropanolamine are not added in the main agent.

[0063] Comparative example 2

[0064] The embodiment provides an etching solution compatible with Cu / Mo and Cu / MTD, and the preparation raw materials are consistent with those in the embodiment 1 except that isopropanolamine is not added in the main agent, and part of the isopropanolamine is distributed to ammonia (ammonia water is formed, and the molar amount is equal).

[0065] Comparative example 3

[0066] The embodiment provides an etching solution compatible with Cu / Mo and Cu / MTD, and the preparation raw materials are consistent with those in the embodiment 1 except that triethanolamine is not added in the main agent, and part of the triethanolamine is distributed to ammonia (ammonia water is formed, and the molar amount is equal).

[0067] Effect test:

[0068] The products provided in the embodiment 1-9 and the comparative examples 1-3 are tested, the main agent is used for etching a metal film layer (Cu-Mo and Cu-MTD), 1.50% of the auxiliary agent by weight of the main agent is added to the system every time the copper ion is increased by 1000 ppm in the etching process, the etching temperature (30 DEG C) is controlled, and the etching is completed, and then the etching performance is confirmed by using a SEM analysis device, wherein the Cu-Mo etching image in the embodiment 1 is as shown in Figure 1 , and the Cu-MTD etching image is as shown in Figure 2 .

[0069] The results are as follows:

[0070]

[0071]

[0072] It can be found from the above data that the product provided by the embodiment can effectively compatible with Cu / Mo and Cu / MTD two different metal structures, the etching effect is equivalent, and good etching effect can be achieved on different metal film layers, the etching problem caused by poor compatibility of the etching solution is reduced, and the yield of the product is improved; it can be found by comparing the embodiment 1-9 and the comparative examples 1-3 that the compatibility of the product can be effectively improved by selecting specific organic alkali, organic acid and other components compared with other technical solutions, so that the etching effect is more close.

[0073] The application is not limited to the above-mentioned embodiments, and does not mean that the application must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the application, equivalent replacement of each raw material of the product of the application, addition of auxiliary ingredients, selection of specific modes, etc. fall within the protection scope and disclosure scope of the application.

[0074] The preferred embodiments of the application are described in detail above, but the application is not limited to the specific details in the above-mentioned embodiments. Within the technical concept scope of the application, various simple modifications can be made to the technical solutions of the application, and these simple modifications all belong to the protection scope of the application.

[0075] In addition, it should be noted that each specific technical feature described in the above-mentioned specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the application will not further describe various possible combination manners.

Claims

1. An etching solution compatible with Cu / Mo and Cu / MTD, characterized by, The etching solution comprises a main agent and an auxiliary agent; The main agent comprises, in parts by weight, 5-22 parts of an oxidizing agent, 1-15 parts of an organic acid, 0.01-5 parts of an inorganic acid, 0.5-15 parts of an organic base, 0.01-5 parts of a stabilizer, 0.01-1 part of a metal inhibitor, and 1-100 parts of water; The auxiliary agent comprises, in parts by weight, 5-50 parts of an organic acid, 0.01-5 parts of an inorganic acid, 0.5-30 parts of an organic base, 0.01-5 parts of a stabilizer, 0.01-2 parts of a metal inhibitor, and 1-100 parts of water.

2. The etching solution compatible with Cu / Mo and Cu / MTD according to claim 1, wherein The main agent comprises, in parts by weight, 6-20 parts of an oxidizing agent, 1.5-10 parts of an organic acid, 0.01-3 parts of an inorganic acid, 1-10 parts of an organic base, 0.05-1 part of a stabilizer, 0.01-0.05 part of a metal inhibitor, and 1-100 parts of water; Preferably, the auxiliary agent comprises, in parts by weight, 10-40 parts of an organic acid, 0.01-3 parts of an inorganic acid, 2-20 parts of an organic base, 0.05-1 part of a stabilizer, 0.01-1.5 parts of a metal inhibitor, and 1-100 parts of water.

3. The etching solution compatible with Cu / Mo and Cu / MTD according to claim 1 or 2, wherein The oxidizing agent comprises hydrogen peroxide.

4. The etching solution compatible with Cu / Mo and Cu / MTD according to any one of claims 1 to 3, characterized in that, The organic acid in the main agent and the auxiliary agent is independently selected from any one or a combination of at least two of acetic acid, malonic acid, succinic acid, malic acid, citric acid, valeric acid, glycine, tartaric acid, salicylic acid, succinic acid, or isethionic acid, preferably a combination of malonic acid, malic acid, and citric acid.

5. The etching solution compatible with Cu / Mo and Cu / MTD according to any one of claims 1 to 4, wherein The inorganic acid in the main agent and the auxiliary agent is independently selected from any one or a combination of at least two of hydrochloric acid, sulfuric acid, phosphoric acid, or nitric acid, preferably phosphoric acid.

6. The etching solution compatible with Cu / Mo and Cu / MTD according to any one of claims 1 to 5, wherein The organic base in the main agent and the auxiliary agent is independently selected from any one or a combination of at least two of ethylenediamine, diethylaminopropylamine, propylenediamine, triethanolamine, diethanolamine, dimethyl ethanolamine, isopropanolamine, tris-hydroxymethyl aminomethane, isobutanolamine, or triethanolamine, preferably a combination of triethanolamine and isopropanolamine.

7. The etching solution compatible with Cu / Mo and Cu / MTD according to any one of claims 1 to 6, wherein The stabilizer in the main agent and the auxiliary agent is independently selected from any one or a combination of at least two of phenylurea, p-hydroxybenzenesulfonic acid, glycerol, propylene glycol, ethylene glycol, ethylene glycol monobutyl ether, diethylene glycol, or 1,2-propanediol.

8. The etching solution compatible with Cu / Mo and Cu / MTD according to any one of claims 1 to 7, wherein The metal inhibitor in the main agent and the auxiliary agent is independently selected from any one or a combination of at least two of 2-sulfur furan, pyrrolidine, tetraoxypyrimidine, 5-(thiophene-2-yl)-1H-tetrazole, 6-amino purine, methyl piperazine, hydroxyethyl piperazine, benzotriazole, 3-amino triazole, 5-amino tetrazole, or methyl tetrazole.

9. The etching solution compatible with Cu / Mo and Cu / MTD according to any one of claims 1 to 8, wherein The main agent and / or the auxiliary agent further comprises, in parts by weight, 0.01-10 parts of a surfactant; Preferably, the surfactant in the main agent and the auxiliary agent is independently selected from any one or a combination of at least two of polyethylene glycol, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, sorbitan fatty acid ester, or octadecylamine polyoxyethylene ether.

10. Use of the Cu / Mo and Cu / MTD compatible etching solution according to any one of claims 1-9 in a Cu / Mo and Cu / MTD etching process.

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