Etching liquid composition

Abstract

Disclosed is an etchant composition capable of ensuring that an upper film of a metal wiring film is free of recesses and tips. One aspect of the present invention provides an etchant composition comprising: an inorganic acid; an organic acid; a sulfonic acid compound; a cyclic compound; a sugar alcohol; and a fluorine-based compound.

Description

Technical Field

[0001] The present invention relates to an etching liquid composition, in particular to an etching liquid composition for etching a metal wiring film. Background Art

[0002] With the development of the display screen field for visually expressing various electrical signal information, various flat panel display devices with excellent characteristics such as thinner, lighter, and lower power consumption have been developed.

[0003] In addition, as the display area of ​​display devices is gradually increasing, various wirings and electrodes included in the display devices need to be formed of materials with as low specific resistance as possible. For this reason, various wirings and electrodes included in the display devices may include metal.

[0004] In addition, various wirings and electrodes included in the display device can be formed using patterning processes such as photolithography processes including etching processes. When the wirings and electrodes are composed of multilayer films with different properties, there will be certain limitations in obtaining wirings and electrodes with desired characteristics through etching processes. Summary of the invention

[0005] An object of the present invention is to provide an etching solution composition which has an excellent etching profile of a metal wiring film after etching.

[0006] Another object of the present invention is to provide an etching solution composition which, when the metal wiring film is a multi-layer film, has no concavity or tip in the upper film and can minimize undercut of the lower film.

[0007] Another object of the present invention is to provide a method for etching a metal wiring film using the etching solution composition.

[0008] The purpose of the present invention is not limited to the purpose mentioned in the above content. The following description will help to understand other purposes and advantages of the present invention that are not mentioned, and can be further clarified through the embodiments of the present invention. In addition, the purpose and advantages of the present invention can be easily implemented by the methods and combinations thereof described in the claims.

[0009] In order to achieve the above-mentioned purpose, the first aspect of the present invention provides an etching solution composition, comprising: an inorganic acid; an organic acid; a sulfonic acid compound; a cyclic compound; a sugar alcohol; and a fluorine compound.

[0010] In a second aspect of the present invention, based on the first aspect, the weight ratio of the sugar alcohol to the fluorine compound can be 1:0.01 to 1:2.

[0011] In a third aspect of the present invention, based on the first or second aspect, a weight ratio of the sulfonic acid compound to the sugar alcohol may be 1:0.2 to 1:10.

[0012] In a fourth aspect of the present invention, based on any one of the first to third aspects, a weight ratio of the inorganic acid to the sugar alcohol may be 1:0.1 to 1:5.

[0013] According to a fifth aspect of the present invention, in addition to any one of the first to fourth aspects, the inorganic acid may include one or more selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, and boric acid.

[0014] According to a sixth aspect of the present invention, in addition to any one of the first to fifth aspects, the organic acid may contain two or more carboxyl groups.

[0015] In the seventh aspect of the present invention, based on any one of the first to sixth aspects, the organic acid may include one or more selected from the group consisting of oxalic acid, formic acid, acrylic acid, lactic acid, amino acids, propionic acid, benzoic acid, salicylic acid, malic acid, benzoic acid and fatty acids.

[0016] According to an eighth aspect of the present invention, in addition to the first to seventh aspects, the sulfonic acid compound may include one or more of an aliphatic compound and an aromatic compound.

[0017] In the ninth aspect of the present invention, the sulfonic acid compound may include one or more of methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid.

[0018] According to a tenth aspect of the present invention, in addition to any one of the first to ninth aspects, the cyclic compound may contain two or more nitrogen atoms.

[0019] According to an eleventh aspect of the present invention, based on any one of the first to tenth aspects, the cyclic compound may include one or more of benzotriazole, aminomercaptotriazole, methyltetrazole, imidazole, aminotetrazole and benzothiazole.

[0020] According to a twelfth aspect of the present invention, in addition to any one of the first to eleventh aspects, the sugar alcohol may include a chain compound.

[0021] According to a thirteenth aspect of the present invention, in any one of the first to twelfth aspects, the sugar alcohol may have 4 or more carbon atoms.

[0022] According to a fourteenth aspect of the present invention, based on any one of the first to thirteenth aspects, the sugar alcohol may include one or more of sorbitol, mannitol, galactitol, iditol, xylitol and erythritol.

[0023] In the fifteenth aspect of the present invention, based on any one of the first to fourteenth aspects, the fluorine compound may include one or more selected from the group consisting of NH4HF2, NH4F, HF, NaHF2, NaF, KHF2, KF and NH4BF4.

[0024] According to the sixteenth aspect of the present invention, based on any one of the first to fifteenth aspects, the etching solution composition may contain: 0.5 to 9.6 weight % of an inorganic acid; 0.1 to 1.0 weight % of an organic acid; 0.30 to 1.5 weight % of a sulfonic acid compound; 0.10 to 0.55 weight % of a cyclic compound; 0.1 to 5.0 weight % of a sugar alcohol; and 0.05 to 0.20 weight % of a fluorine compound.

[0025] The above-mentioned means for solving the above-mentioned problems do not list all the features of the present invention. Various features of the present invention and their advantages and effects can be understood in detail through the following specific embodiments.

[0026] According to one aspect of the present invention, an etching liquid composition having an excellent etching profile of a metal wiring film after etching can be provided.

[0027] Another aspect of the present invention provides an etching solution composition which, when a metal wiring film is a multi-layer film, has no concavity or sharp edge in the upper film and can minimize the side etching of the lower film.

[0028] In addition to the effects described above, specific effects of the present invention will be described in the following description of specific contents for implementing the invention. DETAILED DESCRIPTION

[0029] Unless the context clearly indicates otherwise, singular terms in this specification also include the plural term.

[0030] In this specification, the numerical range represented by the term "to" represents a numerical range that includes the values ​​recorded before and after the term as the lower limit and the upper limit, respectively. In the case where the numerical values ​​of the upper limit and the lower limit of multiple arbitrary numerical ranges are disclosed respectively, the numerical range disclosed in this specification can be understood as an arbitrary numerical range that uses any one of the multiple lower limits and any one of the multiple upper limits as the lower limit and the upper limit, respectively. For example, when recorded as a to b or c to d in the specification, it can be understood as being recorded as more than a and less than b, more than a and less than d, more than c and less than d, or more than c and less than b.

[0031] 1. Etching liquid composition

[0032] In one aspect of the present invention, an etching liquid composition is provided, comprising: an inorganic acid; an organic acid; a sulfonic acid compound; a cyclic compound; a sugar alcohol; and a fluorine compound. In one aspect of the present invention, when a metal wiring film is etched using the etching liquid composition comprising an inorganic acid, an organic acid, a sulfonic acid compound, a cyclic compound, a sugar alcohol, and a fluorine compound, even if the content of the fluorine compound is reduced, the upper metal wiring film can be prevented from having a concave and a sharp tip, and the side etching of the lower metal wiring film can be minimized.

[0033] Next, the configuration of the present invention will be described in more detail.

[0034] Inorganic acid

[0035] The inorganic acid according to the present invention can function as an oxidizing etchant for etching a metal wiring film of one or more of indium gallium zinc oxide (IGZO), Cu, and indium tin oxide (ITO).

[0036] The content of the inorganic acid according to the present invention can be 0.5 wt % to 9.6 wt %, 0.5 wt % to 9.5 wt %, 0.6 wt % to 9.0 wt %, 0.7 wt % to 8.0 wt %, 0.8 wt % to 7.0 wt %, 0.8 wt % to 6.0 wt %, 0.8 wt % to 5.0 wt %, 0.9 wt % to 4.0 wt %, 0.9 wt % to 3.0 wt %, 0.9 wt % to 2.0 wt %, 0.9 wt % to 1.5 wt % or 0.9 to 1.0 wt % based on the total weight of the etching solution composition. If the content of the inorganic acid according to the present invention is less than the numerical range, the problem of ITO tip may occur, and if it exceeds the numerical range, the problem of ITO concave may occur.

[0037] In some embodiments of the present invention, the inorganic acid may include one or more selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid and boric acid, and specifically, may include nitric acid. In some embodiments of the present invention, by using nitric acid as the inorganic acid, the effect of further reducing IGZO side corrosion can be achieved.

[0038] In some other embodiments of the present invention, the inorganic acid may be one or more salts selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid and boric acid. In this case, the cation in the salt may be potassium, sodium or ammonia.

[0039] Organic Acid

[0040] The organic acid according to the present invention can selectively oxidatively etch IGZO and ITO films without etching Cu. In addition, the organic acid can adjust the etching rate while adjusting the taper angle of the metal film.

[0041] The content of the organic acid according to the present invention can be 0.1 wt % to 1.0 wt %, 0.2 wt % to 0.9 wt %, 0.3 wt % to 0.8 wt %, 0.4 wt % to 0.7 wt % or 0.5 wt % to 0.6 wt % based on the total weight of the etching solution composition. Specifically, when the content of the organic acid is less than the numerical range, the problem of ITO tip after etching may occur, and when it exceeds the numerical range, the problem of ITO concave after etching may occur.

[0042] In some embodiments of the present invention, the organic acid may contain two or more carboxyl groups. Specifically, by making the organic acid contain two or more carboxyl groups, the effect of reducing the IGZO side erosion while raising the Ti tail to an appropriate level can be better achieved.

[0043] For example, the organic acid may include one or more selected from the group consisting of oxalic acid, formic acid, acrylic acid, lactic acid, amino acids, propionic acid, benzoic acid, salicylic acid, malic acid, benzoic acid and fatty acids, and specifically, may include oxalic acid. In some embodiments of the present invention, by using oxalic acid as the organic acid, the effect of reducing the IGZO side erosion while raising the Ti tail to an appropriate level can be achieved.

[0044] In some other embodiments of the present invention, the organic acid may be one or more salts selected from the group consisting of oxalic acid, formic acid, acrylic acid, lactic acid, amino acids, propionic acid, benzoic acid, salicylic acid, malic acid, benzoic acid and fatty acids. In this case, in the salt, the cation may be potassium, sodium or ammonia, for example, the fatty acid may include unsaturated fatty acids, specifically, may include one or more of oleic acid, palmitoleic acid, myristoleic acid, linoleic acid and arachidonic acid.

[0045] Sulfonic acid compounds

[0046] The sulfonic acid compound according to the present invention can be an oxidative etchant for IGZO, Cu, and ITO films.

[0047] In the present invention, the "sulfonic acid compound" may be defined as a compound that generates sulfonate ions in an aqueous solution.

[0048] The content of the sulfonic acid compound according to the present invention may be 0.30 wt % to 1.5 wt %, 0.40 wt % to 1.4 wt %, 0.4 wt % to 1.3 wt %, 0.4 wt % to 1.2 wt %, 0.5 wt % to 1.0 wt %, 0.5 wt % to 0.9 wt %, 0.5 wt % to 0.8 wt %, 0.5 wt % to 0.7 wt % or 0.5 wt % to 0.6 wt %, based on the total weight of the etching solution composition. Specifically, if the content of the sulfonic acid compound is less than the numerical range, the problem of ITO tip after etching may occur, and if it exceeds the numerical range, the problem of ITO concavity after etching may occur.

[0049] In some embodiments of the present invention, the sulfonic acid compound may include one or more of an aliphatic compound and an aromatic compound. Among them, the aliphatic compound may be a non-cyclic compound having a sulfonic acid group (-SO3H) or a cyclic non-aromatic carbon compound having a sulfonic acid group (-SO3H). In some embodiments of the present invention, by using an aliphatic compound or an aromatic compound as the sulfonic acid compound, compared with aminosulfonic acid, after etching, the ITO tip and the ITO concave do not exist and the Ti tail (Tail) and the IGZO side etching can be better adjusted to an appropriate level. Among them, the aromatic compound may be an aromatic cyclic compound having a sulfonic acid group. For example, the aromatic cyclic compound may include one or more benzene rings having one or more sulfonic acid groups as substituents.

[0050] In some embodiments of the present invention, the sulfonic acid compound may include at least one of an alkyl sulfonic acid and an aromatic sulfonic acid. For example, the alkyl sulfonic acid may be a compound in which R in R-SO3H is a linear or branched alkyl group with a carbon number of 1 to 7. For example, the aromatic sulfonic acid may be a compound in which R in R-SO3H is an aryl group with a carbon number of 6 to 20 or a heteroaryl group with a carbon number of 3 to 20.

[0051] In some embodiments of the present invention, the sulfonic acid compound may include one or more of methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid, and specifically, may include methanesulfonic acid. In some embodiments of the present invention, by using methanesulfonic acid as the sulfonic acid compound, after etching, the ITO tip and the ITO concave do not exist and the Ti tail and the IGZO side etching can be adjusted to an appropriate level.

[0052] Cyclic compounds

[0053] The cyclic compound according to the present invention can reduce the etching rate of IGZO, Ti, Cu and ITO films. In addition, the cyclic compound according to the present invention can selectively etch IGZO, Ti and ITO films by preventing the corrosion of Cu.

[0054] The content of the cyclic compound according to the present invention may be 0.10 wt % to 0.55 wt %, 0.10 wt % to 0.50 wt %, 0.15 wt % to 0.45 wt %, 0.20 wt % to 0.40 wt %, 0.25 wt % to 0.35 wt %, 0.28 wt % to 0.32 wt %, 0.29 wt % to 0.31 wt % or 0.30 wt % to 0.31 wt %, based on the total weight of the etching solution composition. Specifically, if the content of the cyclic compound is less than the numerical range, the problem of ITO concavity after etching may occur, and if it exceeds the numerical range, the problem of ITO tip after etching may occur.

[0055] In some embodiments of the present invention, the cyclic compound may contain more than 2 nitrogen atoms, specifically, may contain more than 3 nitrogen atoms, and more specifically, may contain more than 3 nitrogen atoms in the ring. In some embodiments of the present invention, by using a compound containing more than 3 nitrogen atoms as the cyclic compound, after etching, the ITO tip and the ITO concave do not exist and the Ti tail and the IGZO side etching can be adjusted to an appropriate level, thereby forming an excellent etching profile.

[0056] In some embodiments of the present invention, the cyclic compound may include one or more of benzotriazole, aminomercaptotriazole, methyltetrazolyl, imidazole, aminotetrazolyl and benzothiazole, and specifically, may include benzotriazole. In some embodiments of the present invention, by using benzotriazole as the cyclic compound, the effect of further reducing the side etching of IGZO can be achieved.

[0057] Sugar alcohols

[0058] The sugar alcohol according to the present invention can function as an oxidative etchant for IGZO and ITO films. Specifically, the sugar alcohol can selectively etch only metal oxides without affecting the etching speed of Ti and Cu films. Thus, even when the content of the fluorine compound described later is reduced, the etching speed of the ITO film can be increased, thereby removing the ITO tip after etching.

[0059] The content of the sugar alcohol according to the present invention may be 0.1 wt % to 5.0 wt %, 0.5 wt % to 4.5 wt %, 1.0 wt % to 4.0 wt %, 1.5 wt % to 3.5 wt %, 2.0 wt % to 3.0 wt %, 2.5 wt % to 3.0 wt % or 2.8 to 3.0 wt % based on the total weight of the etching solution composition. Specifically, when the content of the sugar alcohol is less than the numerical range, the problem of ITO tip after etching may occur, and when it exceeds the numerical range, the problem of ITO concave after etching and increased IGZO side etching may occur.

[0060] In some embodiments of the present invention, the sugar alcohol may include a chain compound. Among them, the chain compound is a non-cyclic compound, which may refer to a compound that does not contain a ring structure in the molecule. For example, the chain compound may be a compound containing a carbon chain as a main chain and containing more than 1, more than 2, more than 3, more than 4, more than 5 or more than 6 hydroxyl groups on the side chain. Specifically, the number of carbons in the carbon chain may be more than 5 or more than 6. In some embodiments of the present invention, when the number of carbons in the main chain is more than 5 and the number of hydroxyl groups is more than 5, the effect of reducing the side corrosion of IGZO while raising the Ti tail to an appropriate level can be better achieved.

[0061] In some embodiments of the present invention, the carbon number of the sugar alcohol may be 4 or more, specifically, 5 or more, and more specifically, 6 or more. In some embodiments of the present invention, by making the carbon number of the sugar alcohol satisfy the numerical range, the effect of reducing the IGZO side erosion while raising the Ti tail to an appropriate level can be better achieved.

[0062] In some embodiments of the present invention, the sugar alcohol may include one or more of sorbitol, mannitol, galactitol, iditol, xylitol and erythritol, and specifically, may include sorbitol. In some embodiments of the present invention, by using sorbitol as the sugar alcohol, the effect of reducing the IGZO side erosion while raising the Ti tail to an appropriate level can be better achieved.

[0063] Fluorine compounds

[0064] The fluorine-based compound according to the present invention can function as an oxidation etchant for IGZO, Ti, and ITO films.

[0065] According to the present invention, the content of the fluorine compound can be 0.05 wt % to 0.20 wt %, 0.06 wt % to 0.18 wt %, 0.07 wt % to 0.15 wt %, 0.08 wt % to 0.14 wt %, 0.09 wt % to 0.13 wt %, 0.10 wt % to 0.12 wt % or 0.10 wt % to 0.11 wt % based on the total weight of the etching solution composition. Specifically, when the content of the fluorine compound is less than the numerical range, the problem of the presence of the ITO tip after etching and the increase of the IGZO side etching may occur, and when the numerical range is exceeded, the problem of the Ti tail not being able to be fully increased and the problem of the increase of the IGZO side etching may occur.

[0066] In some embodiments of the present invention, the fluorine compound may include one or more of a non-metallic salt and a metal salt, specifically, a non-metallic salt. In some embodiments of the present invention, when a non-metallic salt is used as the fluorine compound, the effect of further reducing the IGZO side corrosion can be achieved compared with a metal salt. For example, the fluorine compound may include one or more selected from the group consisting of NH4HF2, NH4F, HF, NaHF2, NaF, KHF2, KF and NH4BF4, specifically, ammonium bifluoride (NH4HF2) may be included. In some embodiments of the present invention, by using ammonium bifluoride (NH4HF2) as the fluorine compound, the effect of reducing the IGZO side corrosion can be better achieved compared with ammonium fluoride (NH4F).

[0067] The relationship between the components

[0068] In some embodiments of the present invention, the weight ratio of the sugar alcohol to the fluorine compound (sugar alcohol: fluorine compound) can be 1: 0.01 to 1: 2, 1: 0.01 to 1: 1, 1: 0.02 to 1: 0.07, 1: 0.02 to 1: 0.06 or 1: 0.03 to 1: 0.05. In some embodiments of the present invention, when the weight ratio of the sugar alcohol to the fluorine compound (sugar alcohol: fluorine compound) satisfies the numerical range, after etching, the ITO tip and the ITO concave are not present and the Ti tail and the IGZO side etching can be adjusted to an appropriate level. Among them, by including sugar alcohol in the etching solution composition, the excellent profile of the etched metal wiring film can be easily formed even when the content of the fluorine compound is reduced.

[0069] In some embodiments of the present invention, the weight ratio of the sulfonic acid compound to the sugar alcohol (sulfonic acid compound: sugar alcohol) can be 1:0.2 to 1:10, 1:0.2 to 1:8 or 1:0.2 to 1:7. In some embodiments of the present invention, when the weight ratio of the sulfonic acid compound to the sugar alcohol satisfies the numerical range, after etching, the ITO tip and the ITO concave do not exist and the Ti tail and the IGZO side etching can be adjusted to an appropriate level.

[0070] In some embodiments of the present invention, the weight ratio of the inorganic acid to the sugar alcohol (inorganic acid: sugar alcohol) can be 1:0.1 to 1:5, 1:0.2 to 1:5, 1:0.31 to 1:4, 1:0.52 to 1:4, 1:1 to 1:3 or 1:2 to 1:3. In some embodiments of the present invention, when the weight ratio of the inorganic acid to the sugar alcohol satisfies the numerical range, after etching, the ITO tip and the ITO concave do not exist and the Ti tail and the IGZO side etching can be adjusted to an appropriate level.

[0071] In some embodiments of the present invention, the etching solution composition may include: 0.5 wt% to 9.6 wt% of inorganic acid; 0.1 wt% to 1.0 wt% of organic acid; 0.30 wt% to 1.5 wt% of sulfonic acid compound; 0.10 wt% to 0.55 wt% of cyclic compound; 0.1 wt% to 5.0 wt% of sugar alcohol; and 0.05 wt% to 0.20 wt% of fluorine compound. By making the content of each component of the composition satisfy the numerical range, after etching, the ITO tip and ITO concave do not exist and the Ti tail and IGZO side etching can be adjusted to an appropriate level.

[0072] The remaining water

[0073] The etching liquid composition according to the present invention may further contain a balance of water in addition to the composition described above. Specifically, the content of the water may be the remaining content in addition to the composition described above. For example, the content of the water may be 80% by weight or more or 90% by weight or less, or 99% or less, or 98% or less, based on the total weight of the etching liquid composition.

[0074] use

[0075] According to some embodiments of the present invention, the etching liquid composition can be used for etching a quadruple film, specifically, for etching an IGZO / Ti / Cu / ITO quadruple film. Specifically, when the etching liquid composition is used to etch the IGZO / Ti / Cu / ITO quadruple film, the upper ITO film has no concave or sharp tip, the side etching of the lower IGZO film is less than 0.15 μm, and the Ti tail is more than 0.30 μm.

[0076] 2. Etching method of metal wiring film

[0077] According to another aspect of the present invention, there is provided a method for etching a metal wiring film, comprising the step of etching the metal wiring film formed on a substrate using the etching solution composition according to some embodiments.

[0078] For example, the substrate may be a glass substrate containing silicon oxide (SiO2) as a main component; or a transparent plastic substrate. Specifically, the plastic substrate may be polyethersulfone (PES), polyacrylate, polyetherimide, polyethylene naphthalate, polyethylene terephthalate, polyphenylene sulfide (PPS), polyarylate, polyimide, polycarbonate, cellulose triacetate, and cellulose acetate propionate (CAP). However, the technical concept of the present invention is not limited thereto, but may be applied to a variety of substrates in the field of display screens.

[0079] The metal wiring film according to the present invention may be a single-layer film or a multi-layer film, specifically, a multi-layer film. Specifically, as a method for forming the metal wiring film, a general deposition method commonly used in the corresponding technical field may be used. For example, the multi-layer film may be a four-layer film of IGZO / Ti / Cu / ITO from bottom to top. In some embodiments of the present invention, when the metal wiring film is etched using the etching liquid composition according to some embodiments, it is possible to achieve the effect that there is no concave and pointed tip on the upper ITO film, the side etching of the lower IGZO film is less than 0.15 μm, and the Ti tail is more than 0.30 μm.

[0080] Next, the embodiments of the present invention will be described in detail so that those having general knowledge in the technical field to which the present invention belongs can easily implement the present invention. However, this is only an example, and the scope of the claims of the present invention is not limited by the following contents.

[0081] In this specification, the terms "about" or "substantially" represent reasonable deviations of the terms whose deformation does not lead to significant changes in the final result. The terms as described above can be interpreted as including at least ±5% or at least ±10% deviations within the range where the deviation does not lead to the meaning of the deformed word becoming invalid.

[0082] [Manufacturing Example 1: Manufacture of Etching Liquid Composition]

[0083] An etching liquid composition having the composition shown in Table 1 below and the balance of water was prepared.

[0084]

Table 1

[0085]

[0086] [Manufacturing Example 2: Manufacture of an etching solution composition having a different type of inorganic acid than in Example 1]

[0087] The etching solution composition was prepared in the same manner as in Example 1, except that nitric acid was replaced with hydrochloric acid (Example 18), sulfuric acid (Example 19), phosphoric acid (Example 20), and boric acid (Example 21).

[0088]

Table 2

[0089]

[0090] [Manufacturing Example 3: Manufacture of an etching solution composition having a different type of organic acid or sulfonic acid compound than Example 1]

[0091] The etching solution composition was prepared in the same manner as in Example 1, wherein oxalic acid was replaced with formic acid (Example 22), lactic acid (Example 23), benzoic acid (Example 24), acrylic acid (Example 25), oleic acid (Example 26), and glycine (Example 27), respectively.

[0092] Furthermore, etching solution compositions were prepared in the same manner as in Example 1, except that methanesulfonic acid was replaced with benzenesulfonic acid (Example 28) and aminosulfonic acid (Example 29).

[0093]

Table 3

[0094]

[0095] [Manufacturing Example 4: Manufacture of an etching solution composition having a different type of cyclic compound, sugar alcohol compound or fluorine compound than in Example 1]

[0096] The etching solution composition was prepared in the same manner as in Example 1, wherein 1,2,3-benzotriazole was replaced by imidazole (Example 30), aminotetrazole (Example 31), benzothiazole (Example 32), and benzoxazole (Example 33), respectively.

[0097] In addition, etching solution compositions were prepared in the same manner as in Example 1, wherein sorbitol was replaced with mannitol (Example 34), galactitol (Example 35), iditol (Example 36), xylitol (Example 37), and erythritol (Example 38), respectively.

[0098] In addition, an etching solution composition was prepared in the same manner as in Example 1, wherein ammonium bifluoride (NH4HF2) was replaced with ammonium fluoride (NH4F, Example 39), hydrogen fluoride (HF, Example 40), sodium dihydrogen fluoride (NaHF2, Example 41), and ammonium fluoroborate (NH4BF4, Example 42), respectively.

[0099]

Table 4

[0100]

[0101]

[0102] [Manufacturing Example 5: Manufacture of Etching Liquid Composition]

[0103] An etching liquid composition having the composition shown in Table 5 below and the balance of water was prepared.

[0104] Furthermore, an etching liquid composition having the composition shown in the following Table 6 and the balance of water was prepared.

[0105]

Table 5

[0106]

[0107]

Table 6

[0108]

[0109] [Test Example: Evaluation of Etching Performance of Etching Liquid Composition]

[0110] IGZO / Ti / Cu / ITO four-layer film (thickness: Afterwards, the deposited four-layer touch was subjected to an etching process (Ti / Cu / ITO etching time overetching (Over Etch) 80%) using the etching solution composition according to the embodiment and the comparative example. At this time, the Ti / Cu / ITO etching endpoint detector (EPD, End Point Detection) that can be distinguished by naked eyes according to the same overetching time (Over Etch TIme) was used for etching, thereby evaluating the etching performance. The following ITO concave, ITO tip, Ti tail and IGZO side etching performance were evaluated using an electron scanning microscope. Specifically, when the ITO tip and ITO concave are 0μm, the Ti tail is more than 0.30μm and the IGZO side etching is less than 0.15μm, it can be evaluated that the etching solution composition has excellent performance at the moment. Among them, when the etching solution composition is used to etch the metal wiring film, the "concave" refers to the poor contour of the overetched concave from the ITO etching surface, and the "tip" refers to the poor contour protruding from the ITO etching surface. The concave and the tip can be distinguished by the difference in the part in contact with the lower copper film. In addition, "tail" refers to the poor profile of the etched surface caused by the difference in etching speed at different positions of the Ti film, and can be judged as excellent when more than 0.3 μm of Ti remains in the part in contact with Cu. The "side etching" can be defined as the profile where the Ti is overetched and recessed more than 0 μm in the part in contact with Cu.

[0111]

Table 7

[0112]

[0113]

Table 8

[0114]

[0115]

Table 9

[0116]

[0117] Referring to Tables 1 to 9, it can be confirmed that the etching solution compositions of Examples 1 to 26 have an ITO tip and an ITO recess of 0 μm, a Ti tail of 0.30 μm or more, and an IGZO side etch of 0.15 μm or less, compared with the etching solution compositions of Comparative Examples 1 to 20.

[0118] Specifically, in Comparative Examples 1 and 2 in which the content of the inorganic acid exceeded 0.5 wt % to 9.6 wt % based on the total weight of the etching solution composition, it was confirmed that either the ITO tip or the ITO recess exceeded 0 μm.

[0119] In Comparative Examples 3 and 4 in which the content of the organic acid exceeded 0.1 wt % to 1.0 wt % based on the total weight of the etching solution composition, it was confirmed that either the ITO tip or the ITO recess exceeded 0 μm.

[0120] In addition, in Comparative Examples 5 and 6 in which the content of the sulfonic acid compound exceeded 0.30 wt % to 1.5 wt % based on the total weight of the etching solution composition, it was confirmed that either the ITO tip or the ITO recess exceeded 0 μm.

[0121] Furthermore, in Comparative Examples 7 and 8 in which the content of the cyclic compound exceeded 0.10 wt % to 0.55 wt % based on the total weight of the etching solution composition, it was confirmed that either the ITO tip or the ITO recess exceeded 0 μm.

[0122] In addition, in Comparative Examples 9 and 10, where the content of sugar alcohol exceeded 0.1 wt % to 5.0 wt % based on the total weight of the etching solution composition, it was confirmed that one of the ITO tip and the ITO concave exceeded 0 μm. More specifically, in Comparative Example 10, the added sugar alcohol content exceeded the appropriate level, which resulted in the problem of insufficient reduction of IGZO side etching.

[0123] From another point of view, in Comparative Examples 11 and 12, where the content of sugar alcohol meets the appropriate level range and the content of fluorine compounds based on the total weight of the etching solution composition does not meet the range of 0.05 wt % to 0.20 wt %, the problem of one of the ITO tip and the ITO concave exceeding 0 μm and the IGZO side etching cannot be fully reduced.

[0124] From another point of view, in Comparative Examples 13 and 14, where the content of the sugar alcohol does not meet the appropriate level range and the content of the fluorine compound based on the total weight of the etching solution composition does not meet 0.05 wt % to 0.20 wt %, the problem of one of the ITO tip and the ITO concave exceeding 0 μm may occur. More specifically, in Comparative Example 13, where the content of the sugar alcohol does not meet the appropriate range and the content of the fluorine compound exceeds the appropriate range, the problem of the Ti tail not meeting 0.30 μm or more may occur.

[0125] From another point of view, in Comparative Example 15 in which hydrogen peroxide was used instead of the inorganic acid, there was a possibility that the ITO tip exceeded 0 μm.

[0126] From another point of view, in Comparative Examples 16 and 17 using glycerol (three -OH groups) and diethylene glycol (two -OH groups), respectively, there is a possibility that the ITO tip exceeds 0 μm.

[0127] From another viewpoint, in Comparative Examples 18 to 20, which do not contain any of the organic acid, the sulfonic acid compound, and the cyclic compound, there is a possibility that one of the ITO tip and the ITO recess exceeds 0 μm.

[0128] From the viewpoint of the inorganic acid type, when comparing Example 1 with Examples 18 to 21, the effect of further reducing the side corrosion of IGZO can be achieved by using nitric acid as the inorganic acid.

[0129] From the viewpoint of the type of organic acid, by using oxalic acid having two carboxyl groups as the organic acid, it is possible to achieve the effect of reducing the side corrosion of IGZO while raising the Ti tail to an appropriate level.

[0130] From the perspective of the sulfonic acid compound type, when comparing Example 1 with Examples 28 and 29, by using methanesulfonic acid as the sulfonic acid compound, the ITO tip and ITO concave are both 0 μm, the Ti tail is greater than 0.30 μm, and the IGZO side etch is less than 0.15 μm.

[0131] From the viewpoint of the type of cyclic compound, when comparing Example 1 with Examples 30 to 33, the effect of further reducing the side etching of IGZO can be achieved by using benzotriazole as the cyclic compound.

[0132] From the perspective of the sugar alcohol type, when comparing Example 1 with Examples 34 to 38, when the carbon number of the sugar alcohol is 6 or more, the effect of increasing the Ti tail to an appropriate level while reducing IGZO side etching can be better achieved.

[0133] From the perspective of the type of fluorine compounds, when comparing Example 1 with Examples 39 to 42, the effect of reducing IGZO side corrosion can be better achieved by using NH4HF2 as the fluorine compound.

[0134] The preferred embodiments of the present invention are described in detail in the above content, but the scope of the claims of the present invention is not limited thereby, and various deformations and improved forms of the basic concepts of the present invention defined in the attached claims by relevant practitioners are included in the scope of the claims of the present invention.

Claims

1. An etching solution composition comprising: Inorganic acids; Organic acids; Sulfonic acid compounds; Cyclic compounds; Sugar alcohols; and, Fluorine compounds.

2. The etching solution composition according to claim 1, The weight ratio of the sugar alcohol to the fluorine compound is 1:0.01 to 1:

2.

3. The etching solution composition according to claim 1, The weight ratio of the sulfonic acid compound to the sugar alcohol is 1:0.2 to 1:

10.

4. The etching solution composition according to claim 1, The weight ratio of the inorganic acid to the sugar alcohol is 1:0.1 to 1:

5.

5. The etching solution composition according to claim 1, The inorganic acid includes one or more selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, and boric acid.

6. The etching solution composition according to claim 1, The organic acid contains two or more carboxyl groups.

7. The etching solution composition according to claim 1, The organic acid includes one or more selected from the group consisting of oxalic acid, formic acid, acrylic acid, lactic acid, amino acids, propionic acid, benzoic acid, salicylic acid, malic acid, benzoic acid, and fatty acids.

8. The etching solution composition according to claim 1, The sulfonic acid compound includes one or more of an aliphatic compound and an aromatic compound.

9. The etching solution composition according to claim 1, The sulfonic acid compound includes one or more of methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid.

10. The etching solution composition according to claim 1, The cyclic compound contains two or more nitrogen atoms.

11. The etching solution composition according to claim 1, The cyclic compound includes one or more of benzotriazole, aminomercaptotriazole, methyltetrazole, imidazole, aminotetrazole and benzothiazole.

12. The etching solution composition according to claim 1, The sugar alcohol includes a chain compound.

13. The etching solution composition according to claim 1, The sugar alcohol has 4 or more carbon atoms.

14. The etching solution composition according to claim 1, The sugar alcohol includes one or more of sorbitol, mannitol, galactitol, iditol, xylitol and erythritol.

15. The etching solution composition according to claim 1, The fluorine compound includes one or more selected from the group consisting of NH4HF2, NH4F, HF, NaHF2, NaF, KHF2, KF and NH4BF4.

16. The etching solution composition according to claim 1, The etching solution composition comprises: 0.5 wt % to 9.6 wt % of said inorganic acid; 0.1 wt % to 1.0 wt % of said organic acid; 0.30 wt % to 1.5 wt % of the sulfonic acid compound; 0.10 wt % to 0.55 wt % of the cyclic compound; 0.1 wt % to 5.0 wt % of said sugar alcohol; and, 0.05 wt % to 0.20 wt % of the fluorine compound.

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