Etching solution composition for synchronously etching copper-based metal film and amorphous silicon film

Abstract

The invention relates to the technical field of etching solutions, in particular to an etching solution composition for synchronously etching a copper-based metal film and an amorphous silicon film, which comprises hydrogen peroxide, fluoride, a fluorine-containing surfactant, an amide compound, a nitrogen-containing heterocyclic ring compound, a hydroxy acid or carbonyl acid compound, an alcohol amine compound and water. The etching liquid composition satisfies the following conditions: 0.1 < = M + N < = 1, and 2 < = N / M < = 5. According to the invention, the hydrogen peroxide, the fluoride, the fluorine-containing surfactant, the amide compound, the nitrogen-containing heterocyclic ring compound, the hydroxy acid or carbonyl acid compound and the alcohol amine compound are used as main components, and the content relationship between the fluoride and the fluorine-containing surfactant is limited; the etching liquid composition can maintain excellent etching characteristics in the initial, middle and last periods of the service life, the effect of controlling etching of a semiconductor amorphous silicon film is achieved, the subsequent step of dry etching of the amorphous silicon film in a conventional manufacturing process is omitted, the production and manufacturing efficiency is greatly improved, and the manufacturing cost is reduced.

Description

Technical Field

[0001] This invention relates to the field of etching solution technology, and more specifically to an etching solution composition for simultaneous etching of copper-based metal films and amorphous silicon films. Background Technology

[0002] In recent years, with the market demanding high resolution, large area, and 3D display capabilities for TFT-LCD panels, a corresponding requirement for fast response speeds has emerged. This necessitates increasing the electron transport speed within the TFT structure. Currently, the industry is using low-resistance copper to replace higher-resistance aluminum as the electrode material. However, copper exhibits poor adhesion to glass substrates or insulating films such as silicon oxide, and may diffuse into the lower film, making it difficult to form a single layer of copper as a conductive material. Therefore, commonly used metal conductive lines are typically composed of multilayer alloys, such as copper / molybdenum (Cu-Mo), copper / molybdenum-titanium alloy (Cu-MoTi), copper / titanium (Cu-Ti), and copper / molybdenum-niobium alloy (Cu-MoNb). However, when etching these metal materials with etching solutions, the underlying amorphous silicon semiconductor film cannot be etched, requiring additional dry etching processes to meet the process requirements.

[0003] Patent CN107488856A discloses an etchant composition for simultaneously etching sulfonic acid-based metal films and amorphous silicon films, but its etching characteristics may not be guaranteed towards the end of its etching life. Patent CN115852371A discloses a hydrogen peroxide-based etchant composition for simultaneously etching metal films and amorphous silicon films, but with continued use, the amount of copper and silicon ions dissolved in the solution gradually increases, and the etching depth of the amorphous silicon film may gradually decrease until it disappears. Therefore, there is a need to develop an etchant composition with a long lifespan that simultaneously etches copper-based metal films and amorphous silicon films while exhibiting excellent etching characteristics. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides an etching solution composition for the simultaneous etching of long-life copper-based metal films and amorphous silicon films.

[0005] The present invention adopts the following technical solution:

[0006] An etching solution composition for simultaneous etching of copper-based metal films and amorphous silicon films includes hydrogen peroxide, fluorides, fluorinated surfactants, amide compounds, nitrogen-containing heterocyclic compounds, hydroxy acids or carbonyl acids, alkanolamine compounds, and water;

[0007] The etching solution composition satisfies the following conditions:

[0008] 0.1≤M+N≤1, 2≤N / M≤5;

[0009] Wherein, M is the mass percentage of fluorinated surfactant in the etching solution composition, in wt%;

[0010] N represents the mass percentage of fluoride in the etching solution composition, expressed in wt%.

[0011] The etching solution composition for simultaneous etching of copper-based metal films and amorphous silicon films of the present invention controls the etching of semiconductor amorphous silicon films through the synergistic effect of fluorides and fluorinated surfactants. Fluorides are compounds that can dissociate in aqueous solutions and provide fluoride ions or polyatomic fluoride ions. Fluoride ions react with hydrogen peroxide and silicon ions to form soluble fluorosilicates. The addition of fluorinated surfactants improves the wettability of the etching solution and enhances the etching of the amorphous silicon film. Specifically, the present invention further limits the relationship between the content M of the fluorinated surfactant and the content N of the fluoride to satisfy 0.1≤M+N≤1, 2≤N / M≤5, which controls the etching rate of the amorphous silicon film to a suitable level. When M+N>1, the etching ability of the amorphous silicon film is too strong, the etching rate is too fast, and the etching depth exceeds the specification requirements; when M+N<0.1, the etching ability of the amorphous silicon film is insufficient, the etching rate is slow, and the etching depth is lower than the specification requirements. Meanwhile, since fluorides are the main compounds used for etching amorphous silicon films, and excessively high levels of fluorinated surfactants can adsorb onto the amorphous silicon surface, weakening the etching solution's ability to etch the amorphous silicon, the fluoride content must be higher than the fluorinated surfactant content. Specifically, if N / M > 5, the etching ability of the amorphous silicon film is too strong, the etching rate is too fast, and the etching depth exceeds the specifications; if N / M < 2, the etching ability of the amorphous silicon film is insufficient, the etching rate is slow, and the etching depth is lower than the specifications. Preferably, the etching effect on the amorphous silicon film is better when the relationship between the fluorinated surfactant content M and the fluoride content N satisfies 0.3 ≤ M + N ≤ 0.8 and 2 ≤ N / M ≤ 4.

[0012] Furthermore, the fluoride content in the etching solution composition is 0.08–0.82 wt% by mass; preferably, the fluoride content in the etching solution composition is 0.15–0.5 wt% by mass. The fluoride includes one or more of hydrogen fluoride, sodium fluoride, ammonium fluoride, ammonium hydrogen fluoride, fluoroboric acid, potassium fluoride, potassium hydrogen fluoride, and aluminum fluoride.

[0013] Furthermore, the fluorinated surfactant in the etching solution composition has a mass percentage of 0.018–0.2 wt%; preferably, the fluorinated surfactant in the etching solution composition has a mass percentage of 0.05–0.15 wt%. The fluorinated surfactant includes one or more of perfluoropolyether carboxylic acid, perfluoropolyether ammonium carboxylate, perfluoropolyether sodium carboxylate, and perfluoropolyether alcohol.

[0014] Further, the amide compound in the etching solution composition has a mass percentage of 0.1–3 wt%; preferably, the amide compound in the etching solution composition has a mass percentage of 0.5–2 wt%. The amide compound includes one or more of formamide, acetamide, propionamide, butyramide, acrylamide, polyacrylamide, caprolactam, phenylacetamide, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0015] Further, the nitrogen-containing heterocyclic compound in the etching solution composition is 0.5-5 wt% by mass; preferably, the nitrogen-containing heterocyclic compound in the etching solution composition is 1-3 wt% by mass. The nitrogen-containing heterocyclic compound includes one or more of 5-aminotetrazole, 5-methyltetrazole, benzotriazole, aminotriazole, imidazole, pyrazole, 1,3-thiazole, and 4-methylthiazole.

[0016] Further, the hydroxy acid or carbonyl acid compound in the etching solution composition has a mass percentage of 3-15 wt%; preferably, the mass percentage of the hydroxy acid or carbonyl acid compound in the etching solution composition is 5-12 wt%. The hydroxy acid or carbonyl acid compound includes one or more of lactic acid, mandelic acid, tartaric acid, malic acid, citric acid, salicylic acid, hydroxymalonic acid, 3-hydroxyglutaric acid, α-carbonylglutaric acid, and 2-carbonylsuccinic acid.

[0017] Further, the etching solution composition contains 3-10 wt% of an alkanolamine compound; preferably, the etching solution composition contains 5-8 wt% of an alkanolamine compound. The alkanolamine compound includes one or more of ethanolamine, n-propanolamine, isopropanolamine, 2-N-dibutylaminoethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, diisopropanolamine, and phenylpropanolamine.

[0018] Furthermore, the hydrogen peroxide content in the etching solution composition is 8-25 wt% by mass; preferably, the hydrogen peroxide content in the etching solution composition is 10-20 wt% by mass.

[0019] Furthermore, the copper-based metal film includes copper film, copper and its alloy film, multilayer film of copper and titanium, multilayer film of copper and molybdenum, multilayer film of copper and titanium alloy, or multilayer film of copper and molybdenum alloy.

[0020] The etching solution composition for simultaneous etching of copper-based metal films and amorphous silicon films of the present invention uses hydrogen peroxide, fluorides, fluorinated surfactants, amide compounds, nitrogen-containing heterocyclic compounds, hydroxy acids or carbonyl acids, and alkanolamine compounds as main components, and further limits the content relationship of fluorides and fluorinated surfactants. Through the synergistic effect between the raw materials, the etching solution composition can maintain excellent etching characteristics in the early, middle and late stages of its service life, and play a role in controlling the etching of semiconductor amorphous silicon films. Therefore, the subsequent dry etching step of amorphous silicon films in conventional manufacturing processes can be eliminated, which greatly improves production efficiency and reduces manufacturing costs. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1-2 These are the planar and cross-sectional views obtained by SEM measurement of the substrate after etching with the etching solution composition in Example 1 of this invention and after cutting. Detailed Implementation

[0023] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of the present invention.

[0024] The present invention discloses an etching solution composition for simultaneous etching of copper-based metal films and amorphous silicon films, comprising hydrogen peroxide, fluoride, fluorinated surfactant, amide compound, nitrogen-containing heterocyclic compound, hydroxy acid or carbonyl acid compound, alkanolamine compound and water;

[0025] The etching solution composition satisfies the following conditions:

[0026] 0.1≤M+N≤1, 2≤N / M≤5;

[0027] Wherein, M is the mass percentage of fluorinated surfactant in the etching solution composition, in wt%;

[0028] N represents the mass percentage of fluoride in the etching solution composition, expressed in wt%.

[0029] The etching solution composition for simultaneous etching of copper-based metal films and amorphous silicon films of the present invention controls the etching of semiconductor amorphous silicon films through the synergistic effect of fluorides and fluorinated surfactants. Fluorides are compounds that can dissociate in aqueous solutions and provide fluoride ions or polyatomic fluoride ions. Fluoride ions react with hydrogen peroxide and silicon ions to form soluble fluorosilicates. The addition of fluorinated surfactants improves the wettability of the etching solution and enhances the etching of the amorphous silicon film. Specifically, the present invention further limits the relationship between the content M of the fluorinated surfactant and the content N of the fluoride to satisfy 0.1≤M+N≤1, 2≤N / M≤5, which controls the etching rate of the amorphous silicon film to a suitable level. When M+N>1, the etching ability of the amorphous silicon film is too strong, the etching rate is too fast, and the etching depth exceeds the specification requirements; when M+N<0.1, the etching ability of the amorphous silicon film is insufficient, the etching rate is slow, and the etching depth is lower than the specification requirements. Meanwhile, since fluorides are the main compounds used for etching amorphous silicon films, and excessively high levels of fluorinated surfactants can adsorb onto the amorphous silicon surface, weakening the etching solution's ability to etch the amorphous silicon, the fluoride content must be higher than the fluorinated surfactant content. Specifically, if N / M > 5, the etching ability of the amorphous silicon film is too strong, the etching rate is too fast, and the etching depth exceeds the specifications; if N / M < 2, the etching ability of the amorphous silicon film is insufficient, the etching rate is slow, and the etching depth is lower than the specifications. Preferably, the etching effect on the amorphous silicon film is better when the relationship between the fluorinated surfactant content M and the fluoride content N satisfies 0.3 ≤ M + N ≤ 0.8 and 2 ≤ N / M ≤ 4.

[0030] Specifically, in one embodiment of the present invention, the mass percentage of fluoride in the etching solution composition is 0.08–0.82 wt%; more specifically, the mass percentage of fluoride in the etching solution composition is 0.08 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, or 0.82 wt%; preferably, the mass percentage of fluoride in the etching solution composition is 0.15–0.5 wt%. Fluorides are compounds that can dissociate in aqueous solutions and provide fluoride ions or polyatomic fluoride ions. Fluoride ions can react with hydrogen peroxide and silicon ions to form soluble fluorosilicates. Preferably, the fluorides include one or more of hydrogen fluoride, sodium fluoride, ammonium fluoride, ammonium hydrogen fluoride, fluoroboric acid, potassium fluoride, potassium hydrogen fluoride, and aluminum fluoride.

[0031] Specifically, in one embodiment of the present invention, the fluorinated surfactant in the etching solution composition comprises 0.018–0.2 wt% by mass; more specifically, the fluorinated surfactant in the etching solution composition comprises 0.018 wt%, 0.02 wt%, 0.03 wt%, 0.05 wt%, 0.06 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.11 wt%, 0.12 wt%, 0.14 wt%, 0.15 wt%, 0.16 wt%, 0.18 wt%, 0.19 wt%, or 0.2 wt% by mass; preferably, the fluorinated surfactant in the etching solution composition comprises 0.05–0.15 wt% by mass. Fluorinated surfactants are surfactants with fluorocarbon chains as nonpolar groups, that is, fluorine atoms partially or completely replace hydrogen atoms on hydrocarbon chains. Fluorinated surfactants have high surface activity, high thermodynamic and chemical stability. The addition of this type of surfactant can improve the wettability of the etching solution and enhance the etching of amorphous silicon films. If the content of fluorinated surfactant is too high, it can easily combine with the H or OH groups on the silicon surface through chemical bonds, adsorb onto the silicon surface, and reduce the etching rate of the amorphous silicon. The fluorinated surfactant refers to non-PFAS polyfluorinated or perfluorinated surfactants, including one or more of perfluoropolyether carboxylic acids, perfluoropolyether ammonium carboxylate, perfluoropolyether sodium carboxylate, and perfluoropolyether alcohols.

[0032] Specifically, in one embodiment of the present invention, hydrogen peroxide is used as an oxidant for the metal film. The copper film and its alloy to be etched are first oxidized by hydrogen peroxide to form metal oxides, and then dissolved by acid. The mass percentage of hydrogen peroxide in the etching solution composition is 8-25 wt%; specifically, the mass percentage of hydrogen peroxide is 8 wt%, 9 wt%, 10 wt%, 12 wt%, 13 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 20 wt%, 22 wt%, 23 wt%, or 25 wt%; preferably, the mass percentage of hydrogen peroxide in the etching solution composition is 10-20 wt%.

[0033] Specifically, in one embodiment of the present invention, the amide compound in the etching solution composition has a mass percentage of 0.1–3 wt%; specifically, the mass percentage of the amide compound in the etching solution composition is 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.5 wt%, 0.6 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.3 wt%, 1.5 wt%, 1.6 wt%, 1.8 wt%, 2 wt%, 2.2 wt%, 2.4 wt%, 2.5 wt%, 2.7 wt%, or 3 wt%; preferably, the mass percentage of the amide compound in the etching solution composition is 0.5–2 wt%. The amide compound is a hydrogen peroxide stabilizer. This type of compound binds to free radicals in hydrogen peroxide through its amino group, preventing the free radicals from continuing to attack hydrogen peroxide molecules and causing their decomposition. Specifically, the amide compounds include one or more of formamide, acetamide, propionamide, butyramide, acrylamide, polyacrylamide, caprolactam, phenylacetamide, N,N-dimethylformamide, and N,N-dimethylacetamide. Preferably, the amide compounds include one or more of propionamide, acrylamide, and phenylacetamide.

[0034] Specifically, in one embodiment of the present invention, the mass percentage of nitrogen-containing heterocyclic compounds in the etching solution composition is 0.5-5 wt%; specifically, the mass percentage of nitrogen-containing heterocyclic compounds in the etching solution composition is 0.5 wt%, 0.6 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.4 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.1 wt%, 2.3 wt%, 2.4 wt%, 2.5 wt%, 2.7 wt%, 2.8 wt%, 3 wt%, 3.2 wt%, 3.5 wt%, 3.8 wt%, 4 wt%, 4.2 wt%, 4.5 wt%, 4.8 wt%, or 5 wt%; preferably, the mass percentage of nitrogen-containing heterocyclic compounds in the etching solution composition is 1-3 wt%. Nitrogen-containing heterocyclic compounds refer to heterocyclic compounds containing at least one nitrogen atom in their rings. These compounds control the etching rate ratio between the copper film and other film layers by inhibiting the etching of the copper film, thereby forming a good metallic pattern. The nitrogen-containing heterocyclic compounds include one or more of 5-aminotetrazole, 5-methyltetrazole, benzotriazole, aminotriazole, imidazole, pyrazole, 1,3-thiazole, and 4-methylthiazole. Preferably, the nitrogen-containing heterocyclic compound is 4-methylthiazole or 5-methyltetrazole.

[0035] Specifically, in one embodiment of the present invention, the hydroxy acid or carbonyl acid compound in the etching solution composition has a mass percentage of 3-15 wt%; specifically, the mass percentage of the hydroxy acid or carbonyl acid compound is 3 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%, 10 wt%, 12 wt%, 13 wt%, or 15 wt%; preferably, the mass percentage of the hydroxy acid or carbonyl acid compound in the etching solution composition is 5-12 wt%. Hydroxy acids or carbonyl acids refer to compounds that simultaneously contain hydroxyl (or carbonyl) and carboxyl groups in their molecules; these compounds contain two or more functional groups that can participate in hydrogen bonding, are more soluble in water, and the hydroxyl (carbonyl) group is an electron-withdrawing group, therefore generally more acidic than the parent carboxylic acid, and can also act as a pH buffer. In addition, the outermost electron pairs of these oxygen-containing functional groups can form coordination bonds with metal ions such as copper and molybdenum ions in the etching solution, acting as chelating agents, weakening the catalytic effect of metal ions on the decomposition of hydrogen peroxide, reducing the decomposition rate, and increasing the service life of the etching solution. The hydroxy acid or carbonyl acid compound includes one or more of lactic acid, mandelic acid, tartaric acid, malic acid, citric acid, salicylic acid, hydroxymalonic acid, 3-hydroxyglutaric acid, α-carbonylglutaric acid, and 2-carbonylsuccinic acid. Preferably, the hydroxy acid or carbonyl acid compound is tartaric acid, citric acid, or salicylic acid.

[0036] Specifically, in one embodiment of the present invention, the mass percentage of the alkanolamine compound in the etching solution composition is 3-10 wt%; specifically, the mass percentage of the alkanolamine compound in the etching solution composition is 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%; preferably, the mass percentage of the alkanolamine compound in the etching solution composition is 5-8 wt%. The alkanolamine compound includes one or more of ethanolamine, n-propanolamine, isopropanolamine, 2-N-dibutylaminoethanol (DBAE), N,N-dimethylethanolamine, N,N-diethylethanolamine, diisopropanolamine, and phenylpropanolamine. Preferably, the alkanolamine compound is ethanolamine, isopropanolamine, or phenylpropanolamine.

[0037] Specifically, as one embodiment of the present invention, the copper-based metal film includes a copper film, a copper and its alloy film, a multilayer film of copper and titanium, a multilayer film of copper and molybdenum, a multilayer film of copper and titanium alloy, or a multilayer film of copper and molybdenum alloy. More specifically, the molybdenum alloy may include a single layer of molybdenum or molybdenum and at least one selected from titanium (Ti), tantalum (Ta), chromium (Gr), nickel (Ni), neodymium (Nd), aluminum (Al), palladium (Pd), and indium (In); the titanium alloy may include a single layer of titanium or titanium and at least one selected from molybdenum (Mo), tantalum (Ta), chromium (Gr), nickel (Ni), neodymium (Nd), aluminum (Al), palladium (Pd), and indium (In). The amorphous silicon film also includes amorphous silicon containing dopants, wherein the dopant is boron (B) or phosphorus (P).

[0038] The etching solution composition of the present invention will be further described below with reference to specific embodiments.

[0039] Examples 1-44 and Comparative Examples 1-9

[0040] The etching solution compositions of Examples 1-44 and Comparative Examples 1-9 each comprise the raw material components and contents shown in Table 1, with the balance being water.

[0041] Table 1

[0042]

[0043]

[0044]

[0045]

[0046] To evaluate the etching effect of the etching solution of this invention, hydrogenated amorphous silicon film and copper and its alloy film were first deposited sequentially on a glass substrate using a sputtering method. After exposure and development, a specific resist coating pattern was formed. The glass substrate was then immersed in the etching solutions of the various embodiments and comparative examples at 32°C for etching for 100 seconds. After etching, the substrate was rinsed with deionized water and dried with nitrogen. The performance of the etching solution was evaluated under a scanning electron microscope (SEM) using parameters such as etching cone angle (TA), lateral etching loss (CD Loss), etching solution lifetime (dissolved copper content), and asphalt loss (AS loss).

[0047] The etching taper angle (TA) refers to the inclination of the copper bevel. If the taper angle is too large or too small, cracks will occur during subsequent film deposition due to poor step coverage. The latter will make subsequent film deposition difficult. Therefore, maintaining a suitable taper angle is very important.

[0048] Lateral etch loss (CD Loss) is the difference between the actual size and the expected size of the pattern formed after etching.

[0049] Etching solution life (dissolved copper content) refers to the gradual increase in dissolved copper ions (the main component, but also containing small amounts of other metals) in the etching solution as etching progresses, while the effective components in the etching solution continuously decrease, affecting the performance of the etching solution. Therefore, a long etching solution life is extremely beneficial for reducing costs.

[0050] AS loss refers to the etching depth of the a-Si substrate when the etchant reaches the target CD loss. This is a key indicator, and it is calculated as: AS loss = AS depth (within PR) - AS depth (outside PR). Due to potential measurement errors, the average value of three pairs of depths is taken as the AS loss.

[0051] The evaluation criteria are shown in Table 2.

[0052] Table 2

[0053]

[0054] (1) The test results of Examples 1-28 and Comparative Examples 1-9 are shown in Table 3.

[0055] Table 3

[0056]

[0057] As can be seen from the test results of Examples 1-28 in Table 3, the etching solution composition of the present invention mainly comprises hydrogen peroxide, fluoride, fluorinated surfactant, amide compound, nitrogen-containing heterocyclic compound, hydroxy acid or carbonyl acid compound, and alkanolamine compound. By limiting the content relationship of fluoride and fluorinated surfactant, and through the synergistic effect between the raw materials, the etching solution composition maintains excellent etching characteristics in the early, middle, and late stages of its service life, thus playing a role in controlling the etching of semiconductor amorphous silicon films. Figure 1-2 As shown, the etching solution in Example 1 was used for etching, with an etching cone angle of 61.8°, a lateral etching loss of 0.66 μm, and an AS loss of 16 nm, which achieved the purpose of simultaneously etching copper-based metal films and amorphous silicon films.

[0058] As can be seen from the test results of Example 1 and Comparative Examples 1-9, when the content relationship between fluoride and fluorinated surfactant (M+N or N / M) is too large or too small, the AS loss is not within the acceptable range, making it difficult to achieve the goal of simultaneous etching of copper-based metal films and amorphous silicon films. It is evident that the content of fluoride and fluorinated surfactant in the etching solution composition of the present invention has a strong synergistic effect.

[0059] Comparison of the test results of Example 1 with those of Examples 15-16, 17-18, 19-20, 21-22, 23-24, 25-26, and 27-28 shows that when the relationship between the content M of the fluorinated surfactant and the content N of the fluoride, M+N or N / M, meets the corresponding conditions, preferably, when the content of the fluoride is 0.08-0.82 wt%, the mass percentage of the fluorinated surfactant is 0.018-0.2 wt%, the mass percentage of the amide compound is 0.1-3 wt%, the mass percentage of the nitrogen-containing heterocyclic compound is 0.5-5 wt%, the mass percentage of the hydroxy acid or carbonyl acid compound is 3-15 wt%, the mass percentage of the alkanolamine compound is 3-10 wt%, and the mass percentage of the hydrogen peroxide is 8-25 wt%, the etching solution composition can control the etching of the semiconductor amorphous silicon film and achieve synchronous etching of the copper-based metal film and the amorphous silicon film.

[0060] (2) The test results of Examples 1 and Examples 29-31 are shown in Table 4.

[0061] Table 4

[0062]

[0063]

[0064] As can be seen from the test results of Examples 1 and 29-31, the etching solution composition of the present invention, using different fluorinated surfactants, can control the etching of semiconductor amorphous silicon films when the content of the fluorinated surfactant M and the content of fluoride N satisfy the corresponding relationship, and at the same time has excellent etching effect.

[0065] (3) The test results of Examples 1 and Examples 32-34 are shown in Table 5.

[0066] Table 5

[0067]

[0068] As can be seen from the test results of Examples 1 and 32-34, the etching solution composition of the present invention, using different fluorides, can control the etching of semiconductor amorphous silicon films when the content of fluorinated surfactant M and the content of fluoride N satisfy the corresponding relationship, and at the same time has excellent etching effect.

[0069] (4) The test results of Examples 1 and Examples 35-37 are shown in Table 6.

[0070] Table 6

[0071]

[0072] As can be seen from the test results of Examples 1 and 35-37, the etching solution composition of the present invention, using different amide compounds, can control the etching of semiconductor amorphous silicon films when the content of fluorinated surfactant M and the content of fluoride N satisfy the corresponding relationship, and at the same time has excellent etching effect.

[0073] (5) The test results of Examples 1 and Examples 38-40 are shown in Table 7.

[0074] Table 7

[0075]

[0076] As can be seen from the test results of Examples 1 and 38-40, the etching solution composition of the present invention, using different nitrogen-containing heterocyclic compounds, can control the etching of semiconductor amorphous silicon films when the content of fluorinated surfactant M and the content of fluoride N satisfy the corresponding relationship, and at the same time has excellent etching effect.

[0077] (6) The test results of Examples 1 and 41-42 are shown in Table 8.

[0078] Table 8

[0079]

[0080] As can be seen from the test results of Examples 1 and 41-42, the etching solution composition of the present invention, using different hydroxy acids or carbonyl acids, can control the etching of semiconductor amorphous silicon films when the content of fluorinated surfactant M and the content of fluoride N satisfy the corresponding relationship, and at the same time has excellent etching effect.

[0081] (7) The test results of Examples 1 and Examples 43-44 are shown in Table 9.

[0082] Table 9

[0083]

[0084] As can be seen from the test results of Examples 1 and 43-44, the etching solution composition of the present invention, using different alkanolamine compounds, can control the etching of semiconductor amorphous silicon films when the content of fluorinated surfactant M and the content of fluoride N satisfy the corresponding relationship, and at the same time has excellent etching effect.

[0085] The present invention has been further described above with reference to specific embodiments. However, it should be understood that the specific description herein should not be construed as limiting the nature and scope of the present invention. Various modifications made to the above embodiments by those skilled in the art after reading this specification are all within the scope of protection of the present invention.

Claims

1. An etching solution composition for simultaneous etching of copper-based metal films and amorphous silicon films, characterized in that, This includes hydrogen peroxide, fluorides, fluorinated surfactants, amides, nitrogen-containing heterocyclic compounds, hydroxy acids or carbonyl acids, alkanolamines, and water; The etching solution composition satisfies the following conditions: 0.1≤M+N≤1, 2≤N / M≤5; Wherein, M is the mass percentage of fluorinated surfactant in the etching solution composition, in wt%; N represents the mass percentage of fluoride in the etching solution composition, expressed in wt%.

2. The etching solution composition for simultaneous etching of copper-based metal films and amorphous silicon films according to claim 1, characterized in that, The etching solution composition satisfies the following conditions: 0.3≤M+N≤0.8, 2≤N / M≤4.

3. The etching solution composition for simultaneous etching of copper-based metal films and amorphous silicon films according to claim 1, characterized in that, The fluoride includes one or more of hydrogen fluoride, sodium fluoride, ammonium fluoride, ammonium hydrogen fluoride, fluoroboric acid, potassium fluoride, potassium hydrogen fluoride, and aluminum fluoride. The fluoride content in the etching solution composition is 0.08–0.82 wt%. Preferably, the fluoride content in the etching solution composition is 0.15 to 0.5 wt%.

4. The etching solution composition for simultaneous etching of copper-based metal films and amorphous silicon films according to claim 1, characterized in that, The fluorinated surfactant includes one or more of perfluoropolyether carboxylic acid, perfluoropolyether ammonium carboxylate, perfluoropolyether sodium carboxylate, and perfluoropolyether alcohol; The fluorinated surfactant in the etching solution composition has a mass percentage of 0.018–0.2 wt%. Preferably, the fluorinated surfactant in the etching solution composition has a mass percentage content of 0.05 to 0.15 wt%.

5. The etching solution composition for simultaneous etching of copper-based metal films and amorphous silicon films according to claim 1, characterized in that, The amide compounds include one or more of formamide, acetamide, propionamide, butyramide, acrylamide, polyacrylamide, caprolactam, phenylacetamide, N,N-dimethylformamide, and N,N-dimethylacetamide; The amide compound in the etching solution composition has a mass percentage content of 0.1-3 wt%. Preferably, the amide compound in the etching solution composition has a mass percentage content of 0.5 to 2 wt%.

6. The etching solution composition for simultaneous etching of copper-based metal films and amorphous silicon films according to claim 1, characterized in that, The nitrogen-containing heterocyclic compounds include one or more of 5-aminotetrazole, 5-methyltetrazole, benzotriazole, aminotriazole, imidazole, pyrazole, 1,3-thiazole, and 4-methylthiazole. The etching solution composition contains nitrogen-containing heterocyclic compounds at a mass percentage of 0.5–5 wt%. Preferably, the nitrogen-containing heterocyclic compound in the etching solution composition is 1-3 wt%.

7. The etching solution composition for simultaneous etching of copper-based metal films and amorphous silicon films according to claim 1, characterized in that, The hydroxy acids or carbonyl acids include one or more of the following: lactic acid, mandelic acid, tartaric acid, malic acid, citric acid, salicylic acid, hydroxymalonic acid, 3-hydroxyglutaric acid, α-carbonylglutaric acid, and 2-carbonylsuccinic acid. The etching solution composition contains 3-15 wt% hydroxy acid or carbonyl acid compounds. Preferably, the hydroxy acid or carbonyl acid compound in the etching solution composition has a mass percentage of 5-12 wt%.

8. The etching solution composition for simultaneous etching of copper-based metal films and amorphous silicon films according to claim 1, characterized in that, The alkanolamine compounds include one or more of ethanolamine, n-propanolamine, isopropanolamine, 2-N-dibutylaminoethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, diisopropanolamine, and phenylpropanolamine. The etching solution composition contains 3-10 wt% alcohol amine compounds by mass. Preferably, the etching solution composition contains 5-8 wt% of an alkanolamine compound.

9. The etching solution composition for simultaneous etching of copper-based metal films and amorphous silicon films according to claim 1, characterized in that, The etching solution composition contains 8-25 wt% hydrogen peroxide by mass. Preferably, the hydrogen peroxide content in the etching solution composition is 10-20 wt%.

10. The etching solution composition for simultaneous etching of copper-based metal films and amorphous silicon films according to claim 1, characterized in that, The copper-based metal film includes copper film, copper and its alloy film, multilayer film of copper and titanium, multilayer film of copper and molybdenum, multilayer film of copper and titanium alloy, or multilayer film of copper and molybdenum alloy.

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