Etching liquid composition

Abstract

Disclosed is an etching liquid composition having excellent etching performance. According to one aspect, there is provided an etching liquid composition comprising: hydrogen peroxide; a phosphate; an amine having at least one or more hydroxyl groups; a fluoride; a tetraazacyclic compound having four nitrogen atoms within the ring; and a triazacyclic compound having three nitrogen atoms within the ring, and the weight ratio of the tetraazacyclic compound to the triazacyclic compound is 1:0.01 or more to 1:1.25 or less.

Description

Technical Field

[0001] This disclosure relates to etching solution compositions. Background Technology

[0002] Thin-film transistors (TFTs) can be used in liquid crystal displays (LCDs) or micro LED (light-emitting diode) displays as circuits that apply specific signals to each pixel for driving. A TFT can be constructed by a gate wiring for transmitting scan signals, a data wiring for transmitting image signals, and pixel electrodes connected to these two wirings.

[0003] A thin-film transistor can be composed of a semiconductor layer forming a channel with a gate electrode, a source electrode as part of a data wiring, and a drain electrode. In this case, the wiring can be composed of a metal film.

[0004] Typically, the manufacturing method of a thin-film transistor may include an etching step in which a metal film, which serves as a wiring material for the gate or source / drain electrodes, is stacked on a glass substrate, and the metal film is etched to realize the lines of the desired electrical circuit. Summary of the Invention

[0005] (Technical issue) According to one aspect of the invention, an etchant composition is provided that can increase the etching rate of a metal film to an appropriate level while achieving a uniform etching profile.

[0006] According to another aspect of the invention, an etching solution composition is provided that can reduce the change in Critical Dimension Bias (CD) as the concentration of copper in the etching solution composition changes.

[0007] According to another aspect of the present invention, an etching solution composition is provided that is free of undercutting and residue and has excellent thermal stability.

[0008] According to another aspect of the present invention, an etching method is provided that improves yield and economy by omitting the dry etching method.

[0009] According to another aspect of the present invention, a method for manufacturing wiring for a display panel is provided.

[0010] The objectives of this invention are not limited to those mentioned above. Other objectives and advantages of this invention not mentioned can be understood from the following description and will become clearer through embodiments of the invention. Furthermore, the objectives and advantages of this invention can be readily achieved by the means and combinations thereof described in the specification.

[0011] (Technical Solution) According to a first aspect of the invention, an etching solution composition is provided, comprising hydrogen peroxide; a phosphate; an amine having at least one or more hydroxyl groups; a fluoride; a tetranitrogen cyclic compound having four nitrogen atoms in the ring; and a trinitrogen cyclic compound having three nitrogen atoms in the ring, wherein the weight ratio of the tetranitrogen cyclic compound to the trinitrogen cyclic compound is 1:0.01 or more to 1:1.25 or less.

[0012] According to a second aspect of the invention, in the first aspect, the content of hydrogen peroxide may be from 5 parts by weight or more to 25 parts by weight or less relative to 100 parts by weight of the etching solution composition.

[0013] According to a third aspect of the invention, in the first or second aspect, the content of the phosphate may be from 0.05 parts by weight to less than 2 parts by weight relative to 100 parts by weight of the etching solution composition.

[0014] According to a fourth aspect of the invention, in any one of the first to third aspects, the content of the amine may be from more than 0.1 parts by weight to less than 1.0 parts by weight relative to 100 parts by weight of the etching solution composition.

[0015] According to a fifth aspect of the invention, in any one of the first to fourth aspects, the content of the fluoride may be from 0.1 parts by weight to less than 1.0 parts by weight relative to 100 parts by weight of the etching solution composition.

[0016] According to a sixth aspect of the invention, in any one of the first to fifth aspects, the content of the tetranitrogen cyclic compound may be from 0.1 parts by weight to less than 1.0 parts by weight relative to 100 parts by weight of the etching solution composition.

[0017] According to a seventh aspect of the invention, in any one of the first to sixth aspects, the content of the triazine cyclic compound may be from 0.01 parts by weight to less than 0.5 parts by weight relative to 100 parts by weight of the etching solution composition.

[0018] According to an eighth aspect of the invention, in any one of the first to seventh aspects, the weight ratio of the amine to the fluoride may be from 1:0.1 or more to 1:3.85 or less.

[0019] According to a ninth aspect of the invention, in any one of the first to eighth aspects, the weight ratio of the tetrazolium cyclic compound to the amine may be from 1:0.1 or more to 1:3.5 or less.

[0020] According to a tenth aspect of the present invention, in any one of the first to ninth aspects, the weight ratio of the triazine cyclic compound to the amine may be from 1:0.5 or more to 1:26 or less.

[0021] According to the eleventh aspect of the present invention, in any one of the first to tenth aspects, an etching solution composition comprising one or more of the group consisting of sulfates, chelating agents having at least one or more acetate groups, and diol compounds can be provided.

[0022] According to the twelfth aspect of the present invention, in the eleventh aspect, the content of the sulfate may be from 0.05 parts by weight to 2 parts by weight or less relative to 100 parts by weight of the etching solution composition.

[0023] According to a thirteenth aspect of the invention, in the eleventh or twelfth aspect, the weight ratio of the sulfate to the phosphate may be from 1:0.05 or more to 1:30 or less.

[0024] According to the fourteenth aspect of the invention, in any one of the eleventh to thirteenth aspects, the content of the chelating agent may be from more than 1 part by weight to less than 5 parts by weight relative to 100 parts by weight of the etching solution composition.

[0025] According to the fifteenth aspect of the invention, in any one of the eleventh to fourteenth aspects, the content of the diol compound may be more than 1 part by weight and less than 5 parts by weight relative to 100 parts by weight of the etching solution composition.

[0026] According to a sixteenth aspect of the invention, in any one of the first to fifteenth aspects, an etching solution composition may be provided that further comprises an additive selected from the group consisting of etching modifiers, surfactants, and combinations thereof.

[0027] The solutions to the problems described herein are not exhaustive of all features of the invention and can be combined with some embodiments described herein. The various features of the invention, and the advantages and effects arising therefrom, can be understood in more detail with reference to the following specific description.

[0028] (Invention Effects) According to one aspect of the invention, it is possible to achieve a uniform etching profile while increasing the etching rate of the metal film to an appropriate level.

[0029] According to another aspect of the present invention, it is possible to reduce the change in CD (critical dimension bias) caused by changes in the copper concentration in the etching solution composition, and to achieve excellent thermal stability without undercutting and residue.

[0030] According to another aspect of the invention, by omitting the dry etching step, an etching method that improves process yield can be achieved.

[0031] According to another aspect of the invention, the use of the etching solution composition of the invention in etching is provided.

[0032] According to another aspect of the present invention, a method for etching a substrate or display wiring is provided, comprising: Step S1: Prepare a substrate comprising a silicon film, a molybdenum alloy film, and a copper film, and form an etch-resistant pattern on the upper portion of the copper film; and Step S2: Etch the substrate or display wiring using the etching composition described in this invention.

[0033] In one or more embodiments, a dry etching method is not used.

[0034] In one or more embodiments, in step S1, the molybdenum alloy film is disposed above or directly above the silicon film, and the copper film is disposed above or directly above the molybdenum alloy film.

[0035] In one or more embodiments, the silicon film is an amorphous silicon film.

[0036] In one or more embodiments, etching is performed using a wet etching method in step S2.

[0037] In addition to the effects described above, specific effects of the present invention will be described below along with the detailed embodiments. Furthermore, the effects of the present invention are not limited to those mentioned above, and can be readily achieved by the means and combinations thereof described in the specification. Detailed Implementation

[0038] In this specification, singular expressions include plural expressions unless the context clearly indicates otherwise.

[0039] In this specification, terms such as “comprising” and / or “including” specify the presence of the shapes, steps, numbers, operations, parts, elements and / or groups of these mentioned, without excluding the presence or addition of more than one other shape, step, number, operation, part, element and / or group of these.

[0040] In this specification, "at least one of a, b and c" may include a, b or c alone, or may include two or more combinations selected from the group consisting of a, b and c.

[0041] In the case of multiple embodiments described in this specification, unless specifically stated otherwise, the various embodiments can be combined. In this case, the effect of the present invention can be defined as including the effects produced in each embodiment as well as the effects produced by the organic combination of the various embodiments. For example, even if embodiments 1 and 2 are described independently in this specification, unless the context clearly indicates otherwise, embodiments 1 and 2 can be organically combined with each other, and the effect of the present invention can include the effects produced by the combination of embodiments 1 and 2.

[0042] In this specification, terms such as “about” or “substantially” indicate a reasonable amount of deviation from the modified terms so that the final result is not significantly changed. These terms may be interpreted as including a deviation of at least ±5% or at least ±10%, provided that the deviation does not change the meaning of the word (term) to the point of invalidity.

[0043] In this specification, the term "to" indicates a numerical range that includes the values ​​described before and after the term as the lower and upper limits, respectively. For example, when "a to b" is stated in the specification, it can be understood as referring to the range from a to b (a~b).

[0044] In this specification, when multiple values ​​for the upper and lower limits of any numerical range are disclosed, the numerical range disclosed in this specification can be understood as any numerical range where any one of the multiple lower limit values ​​and any one of the multiple upper limit values ​​are respectively used as the lower limit and upper limit values. For example, when it is stated that a or above, or b or above; and c or below, or d or below, it can be understood as stating that a or above c, a or above d, b or above c, or b or above d.

[0045] In this specification, "composition" may refer to a mixture of materials comprising the composition, a reaction product formed from the materials of the composition, or a decomposition product. For example, the content of the materials in the composition can be measured using gas chromatography. Specifically, the content of the materials can be analyzed using an Agilent gas chromatograph (product name: Agilent 7890 GC, column: HP-5, carrier gas: helium (flow rate 2.4 mL / min), detector: FID, injection volume: 1 μL, initial value: 70 °C / 4.2 min, final value: 280 °C / 7.8 min, program rate: 15 °C / min).

[0046] According to one aspect of the present invention, an etching solution composition is provided, comprising hydrogen peroxide; a phosphate; an amine having at least one hydroxyl group; a fluoride; a tetranitrogen cyclic compound having four nitrogen atoms in its ring; and a trinitrogen cyclic compound having three nitrogen atoms in its ring, wherein the weight ratio of the tetranitrogen cyclic compound to the trinitrogen cyclic compound is 1:0.01 or more to 1:1.25 or less. According to one aspect of the present invention, by satisfying the organic combination relationship of the composition and adjusting the weight ratio of the tetranitrogen cyclic compound to the trinitrogen cyclic compound, the etching rate of the metal film can be increased to an appropriate level while achieving a uniform etching profile. According to another aspect of the present invention, the change in Critical Dimension Bias (CD) with variations in copper concentration in the etching solution composition can be reduced, resulting in the absence of undercutting and residue, and achieving excellent thermal stability.

[0047] The structure of the present invention will now be described in more detail.

[0048] 1. Etching solution composition hydrogen peroxide According to the present invention, hydrogen peroxide can effectively etch a metal film by oxidizing the metal contained in the metal film. Specifically, when the metal contained in the metal film is copper, hydrogen peroxide can act as an oxidant that effectively oxidizes copper to etch the copper film.

[0049] In some examples, the reaction in which the hydrogen peroxide acts as an oxidant can proceed according to the following reaction formula 1.

[0050]

Reaction Formula 1

[0051] In some embodiments of the present invention, the content of hydrogen peroxide relative to 100 parts by weight of the etching solution composition may be 5 parts by weight or more and 25 parts by weight or less. Specifically, relative to 100 parts by weight of the etching solution composition, the content of hydrogen peroxide may be 5 parts by weight or more, 7 parts by weight or more, 9 parts by weight or more, 11 parts by weight or more, 13 parts by weight or more, 15 parts by weight or more, 17 parts by weight or more, or 19 parts by weight or more; and 20 parts by weight or less, 21 parts by weight or less, 22 parts by weight or less, 23 parts by weight or less, 24 parts by weight or less, or 25 parts by weight or less. In some embodiments of the present invention, by adjusting the content of hydrogen peroxide to the aforementioned numerical range, it is possible to etch the metal film (e.g., a copper film or a copper alloy film) to an appropriate level while achieving a uniform taper angle.

[0052] phosphate In this specification, "phosphate" is defined as a salt that contains at least one phosphate group within its molecule and in which the cation is ionically bonded to the phosphate group.

[0053] The phosphate according to the invention can bind with free radicals generated during the decomposition of hydrogen peroxide to suppress the continuous generation of free radicals. Accordingly, hydrogen peroxide can be stabilized to adjust the taper angle to an appropriate level. That is, the phosphate can effectively prevent a decrease in etching rate during the etching process of copper films.

[0054] In some embodiments of the present invention, the content of the phosphate relative to 100 parts by weight of the etching solution composition may be 0.05 parts by weight or more to 2 parts by weight or less. Specifically, the content of the phosphate relative to 100 parts by weight of the etching solution composition may be 0.05 parts by weight or more, 0.1 parts by weight or more, 0.3 parts by weight or more, or 0.5 parts by weight or more; and 0.6 parts by weight or less, 0.7 parts by weight or less, 1.0 parts by weight or less, 1.5 parts by weight or less, or 2 parts by weight or less. In some embodiments of the present invention, by adjusting the content of the phosphate to the aforementioned numerical range, the etching rate reduction can be effectively prevented during the etching process of the copper film, and the taper angle can be effectively controlled when forming the metal pattern.

[0055] For example, the phosphate is not particularly limited, but specifically may include one or more selected from the group consisting of ammonium monophosphate (ammonium diphosphate), sodium monophosphate, sodium diphosphate, ammonium diphosphate, sodium triphosphate, ammonium triphosphate, and potassium phosphate.

[0056] amine According to the amine of the present invention, by containing one or more hydroxyl groups within the molecule, the pH of the etching solution composition can be increased to slowly regulate the etching rate of the copper film and to improve the etching rate of the molybdenum alloy film. Accordingly, the amine can facilitate the separation of molybdenum ions from the surface of the silicon film to increase the contact time of the etching solution composition with the silicon film, ultimately improving the etching rate of the silicon film to an appropriate level.

[0057] In some embodiments of the present invention, the number of hydroxyl groups within the amine can be one or more, two or more, or three or more, specifically one or more to three or less, i.e., one, two, or three, more specifically two. In some embodiments of the present invention, by adjusting the number of hydroxyl groups within the amine to the stated numerical range, an appropriate level of etching rate can be achieved simultaneously for both the solubility of the amine in the etching solution composition and the molybdenum alloy film and the silicon film. Furthermore, by adjusting the number of hydroxyl groups within the amine to the stated numerical range, copper film, molybdenum alloy film, and silicon film can be etched simultaneously.

[0058] In some examples, the amine is not particularly limited, but specifically may include one or more selected from the group consisting of N-methylethanolamine, monoethanolamine, diethanolamine, dimethylethanolamine, diethylethanolamine, N,N-diisopropylaminoethanol, methyl diethanolamine, and triethanolamine.

[0059] In some embodiments of the present invention, the content of the amine relative to 100 parts by weight of the etching solution composition may be 0.1 parts by weight or more to 1.0 parts by weight or less. Specifically, the content of the amine relative to 100 parts by weight of the etching solution composition may be 0.1 parts by weight or more, 0.2 parts by weight or more, 0.3 parts by weight or more, or 0.35 parts by weight or more; and 0.4 parts by weight or less, 0.5 parts by weight or less, 0.6 parts by weight or less, 0.7 parts by weight or less, 0.8 parts by weight or less, 0.9 parts by weight or less, or 1.0 parts by weight or less. In some embodiments of the present invention, by adjusting the content of the amine to the aforementioned numerical range, the formation of residues and undercuts can be effectively prevented, and the change in CD (critical dimension bias) with changes in copper concentration in the etching solution composition can be reduced.

[0060] In this specification, CD (Critical Dimension Bias) refers to the difference between the CD (Critical Dimension) of the photoresist pattern and the CD of the metal film pattern formed using the photoresist pattern as an etching mask. By confirming the CD bias, it can be determined how much metal has been etched.

[0061] In this manual, the "CD deviation change" can be calculated according to the following mathematical formula 1.

[0062]

Mathematical Formula 1

[0063] Fluorides The fluoride according to the present invention can be used as an etchant for etching at least any one of copper films, molybdenum films, molybdenum alloy films, and silicon films. Specifically, the stronger the acidity of the fluoride, the greater its activity, thereby further improving its effectiveness as an etchant. For example, when the silicon film is an amorphous silicon film, the fluoride can be the main factor in the etching rate of the amorphous silicon film. For example, the fluoride can decompose and etch silicon according to the following reaction formula 2.

[0064]

Reaction 2

[0065] In some examples, the fluoride is not particularly limited, but specifically may include one or more selected from the group consisting of hydrofluoric acid, ammonium fluoride, potassium fluoride, sodium fluoride, ammonium bifluoride, potassium bifluoride, and sodium bifluoride.

[0066] Tetranitrogen cyclic compounds The tetranitrogen cyclic compound according to the present invention, as a corrosion inhibitor for copper films, copper alloy films, molybdenum films, or molybdenum alloy films, can be adsorbed onto the surface of the aforementioned films to adjust the etching rate and contribute to the stabilization of the etching profile according to the contamination concentration. Specifically, during the use of the etching solution composition, when the concentration of copper ions in the etching solution composition increases, the reaction is activated, thereby causing the etching rate to increase excessively. Accordingly, as the CD deviation increases, the CD deviation difference can increase. At this time, the tetranitrogen cyclic compound can effectively suppress the increase of CD deviation even under conditions of increased copper ion concentration.

[0067] In some embodiments of the present invention, the content of the tetranitrogen cyclic compound is, relative to 100 parts by weight of the etching solution composition, from 0.1 parts by weight to 1.0 parts by weight or less. Specifically, relative to 100 parts by weight of the etching solution composition, the content of the tetranitrogen cyclic compound may be 0.1 parts by weight or more, 0.2 parts by weight or more, 0.3 parts by weight or more, 0.4 parts by weight or more, or 0.5 parts by weight or more; and 0.6 parts by weight or less, 0.7 parts by weight or less, 0.8 parts by weight or less, 0.9 parts by weight or less, or 1.0 parts by weight or less. In some embodiments of the present invention, by adjusting the content of the tetranitrogen cyclic compound to the aforementioned numerical range, an appropriate level of CD deviation, a reduction in the amount of CD deviation (Critical Dimension Bias) variation with changes in copper concentration in the etching solution composition, and the absence of residue can be achieved.

[0068] In some embodiments of the present invention, the tetranitrogen cyclic compound may comprise four nitrogen atoms within the ring. For example, the tetranitrogen cyclic compound is not particularly limited, but specifically may comprise one or more of the group consisting of 5-aminotetrazole, 5-methyl-1H-tetrazole, and 5-mercapto-1-methyltetrazole.

[0069] Trinitrogen cyclic compounds The trinitrogen cyclic compound according to the present invention, as a corrosion inhibitor for copper films, copper alloy films, molybdenum films, or molybdenum alloy films, can be adsorbed onto the surface of the aforementioned films to adjust the etching rate and contribute to the stabilization of the etching profile according to the concentration of contaminants. Specifically, during the use of the etching solution composition, when the concentration of copper ions in the etching solution composition increases, the reaction is activated, and the etching rate can excessively increase. Accordingly, the CD deviation difference can increase as the CD deviation increases. At this time, the trinitrogen cyclic compound can effectively suppress the increase of CD deviation even under conditions of increased copper ion concentration. Furthermore, by combining the trinitrogen cyclic compound with the aforementioned tetranitrogen cyclic compound, the effect of preventing corrosion of copper films, copper alloy films, molybdenum films, or molybdenum alloy films can be further improved.

[0070] In some embodiments of the present invention, the content of the triazine cyclic compound is, relative to 100 parts by weight of the etching solution composition, 0.01 parts by weight or more to 0.5 parts by weight or less. Specifically, relative to 100 parts by weight of the etching solution composition, the content of the triazine cyclic compound may be 0.01 parts by weight or more, 0.05 parts by weight or more, or 0.06 parts by weight or more; and 0.1 parts by weight or less, 0.2 parts by weight or less, 0.3 parts by weight or less, 0.4 parts by weight or less, or 0.5 parts by weight or less. In some embodiments of the present invention, by adjusting the content of the triazine cyclic compound to the aforementioned numerical range, an appropriate level of CD deviation, a reduction in the amount of CD deviation (Critical Dimension Bias) variation with changes in copper concentration in the etching solution composition, and the absence of residue can be achieved.

[0071] For example, the trinitrogen cyclic compound is not particularly limited to a compound having three nitrogen atoms in the ring, but specifically may include one or more selected from the group consisting of 1,2,4-triazole, 3-amino-1,2,4-triazole-5-thiol, benzotriazole, 1,2,4-triazole-3-thiol, and 3-mercapto-4-methyl-1,2,4-triazole.

[0072] Relationship between constituent elements In some embodiments of the present invention, the weight ratio of the tetranitrogen cyclic compound to the trinitrogen cyclic compound is 1:0.01 or more to 1:1.25 or less. Specifically, the weight ratio of the tetranitrogen cyclic compound to the trinitrogen cyclic compound may be 1:0.01 or more, 1:0.03 or more, or 1:0.06 or more; and 1:0.15 or less, 1:0.17 or less, 1:0.60 or less, or 1:1.25 or less. In some embodiments of the present invention, by adjusting the weight ratio of the tetranitrogen cyclic compound to the trinitrogen cyclic compound to the aforementioned numerical range, the etching rate of the metal film can be increased to an appropriate level while achieving a uniform etching profile. Furthermore, by adjusting the weight ratio of the tetranitrogen cyclic compound to the trinitrogen cyclic compound to the aforementioned numerical range, the change in Critical Dimension Bias (CD) with variations in copper concentration in the etching solution composition can be reduced, resulting in the absence of undercutting and residue, and achieving excellent thermal stability.

[0073] In some embodiments of the present invention, the weight ratio of the amine to the fluoride may be from 1:0.1 or more to 1:3.85 or less. Specifically, the weight ratio of the amine to the fluoride may be 1:0.1 or more, 1:0.20 or more, 1:0.38 or more, or 1:0.77 or more; and 1:1 or less, 1:2 or less, or 1:3.85 or less. In some embodiments of the present invention, by adjusting the weight ratio of the amine to the fluoride to the aforementioned numerical range, an appropriate level of etching rate for the amorphous silicon film can be achieved while simultaneously eliminating undercutting and residue.

[0074] In some embodiments of the present invention, the weight ratio of the tetranitrogen cyclic compound to the amine may be 1:0.1 or higher and 1:3.5 or lower. Specifically, the weight ratio of the tetranitrogen cyclic compound to the amine may be 1:0.1 or higher, 1:0.25 or higher, 1:0.26 or higher, or 1:0.65 or higher; and 1:0.87 or lower, 1:1 or lower, 1:2 or lower, 1:2.5 or lower, 1:2.6 or lower, or 1:3.5 or lower. In some embodiments of the present invention, by adjusting the weight ratio of the tetranitrogen cyclic compound to the amine to the aforementioned numerical range, the etching rate performance of the amorphous silicon film is further improved, while an appropriate level of CD deviation and a reduction in the amount of CD deviation (Critical Dimension Bias) variation with changes in copper concentration in the etching solution composition can be achieved.

[0075] In some embodiments of the present invention, the weight ratio of the triazine cyclic compound to the amine may be from 1:0.5 or more to 1:26 or less. Specifically, the weight ratio of the triazine cyclic compound to the amine may be 1:0.5 or more, 1:0.52 or more, 1:1.67 or more, 1:3.33 or more, or 1:4.33 or more; and 1:5.20 or less, 1:16.67 or less, or 1:26 or less. In some embodiments of the present invention, by adjusting the weight ratio of the triazine cyclic compound to the amine to the aforementioned numerical range, the increase in CD deviation is effectively prevented, while the contact time of the etchant composition for the silicon film is improved, allowing molybdenum ions to easily separate from the surface of the silicon film. Ultimately, the etching rate of the silicon film can be improved to an appropriate level.

[0076] Additional constituent elements In some embodiments of the present invention, the etching solution composition may further comprise one or more of the group consisting of sulfates, chelating agents having at least one acetate group, and diol compounds.

[0077] The sulfate of the present invention, as an auxiliary oxidant for etching copper films or copper alloy films, can prevent the etching rate from decreasing during the etching process of copper films or copper alloy films and control the taper angle when forming metal patterns.

[0078] In some embodiments of the present invention, the sulfate content relative to 100 parts by weight of the etching solution composition may be 0.05 parts by weight or more to 2 parts by weight or less. Specifically, relative to 100 parts by weight of the etching solution composition, the sulfate content may be 0.05 parts by weight or more, 0.1 parts by weight or more, 0.3 parts by weight or more, or 0.5 parts by weight or more; and 0.7 parts by weight or less, 1.0 parts by weight or less, 1.5 parts by weight or less, or 2.0 parts by weight or less. In some embodiments of the present invention, by adjusting the sulfate content to the aforementioned numerical range, an appropriate level of CD deviation, a reduction in the amount of CD deviation (Critical Dimension Bias) variation with changes in copper concentration within the etching solution composition, and the absence of residue can be achieved.

[0079] For example, the sulfate is not particularly limited, but specifically may include one or more selected from the group consisting of potassium hydrosulfate, ammonium sulfate, and potassium sulfate.

[0080] In some embodiments of the present invention, the weight ratio of the sulfate to the phosphate may be from 1:0.05 or more to 1:30 or less. Specifically, the weight ratio of the sulfate to the phosphate may be 1:0.05 or more, 1:0.07 or more, or 1:0.75 or more; and 1:2.14 or less, 1:2.86 or less, 1:5 or less, 1:10 or less, 1:20 or less, or 1:30 or less. In some embodiments of the present invention, by adjusting the weight ratio of the sulfate to the phosphate to the aforementioned numerical range, the etching rate performance of the amorphous silicon film is further improved, while an appropriate level of CD bias and a reduction in the amount of CD bias (Critical Dimension Bias) variation with changes in copper concentration in the etching solution composition can be achieved.

[0081] The chelating agent according to the present invention, as a ligand that binds with copper ions to form a chelating compound, can effectively control the reaction between hydrogen peroxide and copper ions.

[0082] In this specification, "acetic acid ester group" is defined as including CH3-COO - Group. Here, the atom bonded to the acetate group may be a hydrogen atom or a metal ion.

[0083] In some embodiments of the present invention, the content of the chelating agent relative to 100 parts by weight of the etching solution composition may be 1 part by weight or more and 5 parts by weight or less. Specifically, the content of the chelating agent relative to 100 parts by weight of the etching solution composition may be 1 part by weight or more, 1.2 parts by weight or more, 2.0 parts by weight or more, or 2.3 parts by weight or more; and 3 parts by weight or less, 4 parts by weight or less, or 5 parts by weight or less. In some embodiments of the present invention, by adjusting the content of the chelating agent to the aforementioned numerical range, the CD deviation can be effectively adjusted to an appropriate level.

[0084] For example, the chelating agent is not particularly limited, but specifically may include one or more selected from the group consisting of iminodiacetic acid, ammonium acetate, potassium acetate, ethylenediaminetetraacetic acid, and sodium acetate.

[0085] In this specification, "diol compound" is defined as a diol represented by R-(OH)2. For example, R can be C n H 2n n can be an integer greater than 2.

[0086] In some embodiments of the present invention, the content of the diol compound relative to 100 parts by weight of the etching solution composition may be 1 part by weight or more to 5 parts by weight or less. Specifically, the content of the diol compound relative to 100 parts by weight of the etching solution composition may be 1 part by weight or more, or 2 parts by weight or more; and 3 parts by weight or less, 4 parts by weight or less, or 5 parts by weight or less. In some embodiments of the present invention, by adjusting the content of the diol compound to the aforementioned range, excellent thermal stability and the absence of residue are achieved.

[0087] For example, the diol compound is not particularly limited, but specifically may include one or more selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol.

[0088] In other embodiments of the invention, the etching solution composition may further include one or more additives selected from the group consisting of etching modifiers, surfactants, and combinations thereof.

[0089] The etching modifier according to the present invention can adjust the etching performance by adjusting the pH of the etching solution composition. For example, the etching modifier may include one or more selected from the group consisting of acetate, sodium dihydrogen citrate, disodium hydrogen citrate, disodium hydrogen phosphate, and trisodium citrate, specifically including acetate, more specifically including one or more selected from the group consisting of sodium acetate, ammonium acetate, and potassium acetate, more specifically potassium acetate. In this case, the pH of the acetate is about 5 to 10, thereby slowly adjusting the etching rate of the copper film but increasing the etching rate of the molybdenum alloy film. During this etching process, the lower molybdenum ions are easily separated from the surface of the silicon film, and the increased etching rate of molybdenum increases the contact time of the etching solution composition with the silicon film, thereby increasing the etching rate of the amorphous silicon film to an appropriate level.

[0090] In some embodiments of the present invention, when potassium acetate is used as the etching modifier, the etching rate of the molybdenum alloy film can be further improved while the etching rate of the copper film is slowly adjusted. Accordingly, the etching rate of amorphous silicon films can also be improved.

[0091] In some embodiments of the present invention, the weight ratio of the acetate to the fluoride may be from 1:0.1 or more to 1:20 or less. Specifically, the weight ratio of the acetate to the fluoride may be 1:0.1 or more, about 1:0.4 or more, 1:1 or more, 1:2 or more, 1:3 or more, 1:4 or more, 1:5 or more, 1:6 or more, 1:10 or more, or 1:15 or more; or less than 1:3, less than 1:4, less than 1:5, less than 1:6, less than 1:10, less than 1:15, or less than 1:20. In some embodiments of the present invention, by adjusting the weight ratio of the acetate to the fluoride to the aforementioned range, the change in CD (critical dimension bias) caused by variations in copper concentration in the etching solution composition can be reduced, and an increase in the appropriate taper angle and the appropriate etching rate for the amorphous silicon film can be achieved.

[0092] In some examples, the surfactant is used to reduce the surface tension of the etching solution composition to ensure uniform etching, and may specifically include one or more selected from the group consisting of anionic surfactants, cationic surfactants, zwitterionic surfactants and nonionic surfactants.

[0093] In addition to the combinations described above, in some embodiments of the present invention, the etching solution composition may also contain a balance of purified water. For example, the content of the purified water may vary depending on the content of the combinations described above.

[0094] In some embodiments of the present invention, the temperature change of the etchant composition is measured after heating it at 25 to 35°C for more than 24 hours. The temperature change can be below 3°C, below 2°C, below 1°C, below 0.5°C, below 0.2°C, below 0.1°C, or below 0.01°C. In some embodiments of the present invention, the temperature change of the etchant composition is adjusted to the aforementioned numerical range, so that the activity or reactivity of the etchant does not change, maintaining a uniform etching rate while significantly reducing the residue generation rate.

[0095] 2. Etching method In this specification, the term "layer" or "film," when observed in an area where the layer or film is present, may include not only the case where it is formed entirely in the area, but also the case where it is formed only in a portion of the area. For example, it may be defined as a surface including a layer or film that is flat, non-flat, or a combination thereof; or a continuous, discontinuous, or a combination thereof. For example, when another component is formed directly on top of a component as a layer or film, the coverage of the other component on the surface of the first component may be defined as 1% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 85% or more, 90% or more, 95% or more, or 99% or more. For example, even when a structure containing multiple aggregated particles is formed, it may be defined as a "layer" or "film."

[0096] In this specification, when another component is positioned directly on top of a component, it can be defined as a situation where no component is placed between the two components.

[0097] According to another aspect of the present invention, an etching method is provided, comprising: (S1) preparing a substrate comprising a silicon film, a molybdenum alloy film, and a copper film, wherein an etch-resistant pattern is formed on a portion of the copper film; and (S2) etching the substrate with an etchant composition according to some embodiments. Previously, in the substrate, wet etching methods for etching the silicon film have resulted in low etch rates, necessitating additional dry etching methods. According to another aspect of the present invention, by using an etchant composition according to some embodiments to etch the substrate, the dry etching method can be omitted. Accordingly, the economics of the process and the yield can be improved.

[0098] In some examples, during step (S1), the molybdenum alloy film may be disposed on or directly above the silicon film, and the copper film may be disposed on or directly above the molybdenum alloy film. In some examples, the silicon film may be an amorphous silicon film.

[0099] For example, step (S2) can be a wet etching method.

[0100] According to another aspect of the present invention, a method for manufacturing display wiring can be provided, comprising: (S1) preparing a substrate comprising a silicon film, a molybdenum alloy film, and a copper film, and forming an etch-resistant pattern on a portion of the copper film; and (S2) etching the substrate with an etchant composition according to some embodiments.

[0101] The embodiments of the present invention will be described in detail below so that those skilled in the art can easily implement the present invention. However, these are merely examples, and the scope of the present invention is not limited by the following description.

[0102] [Example of manufacturing preparation: Material preparation] In the table below, sulfate is potassium sulfate (K2SO4), phosphate is ammonium monophosphate, chelating agent is iminodiacetic acid, glycol is triethylene glycol, amine is diethanolamine, fluoride is ammonium bifluoride, tetrazolium cyclic compound is 5-aminotetrazole, trizolium cyclic compound is 1,2,4-triazole, and acetate is potassium acetate.

[0103] [Preparation Example 1: Preparation of Etching Solution Composition] An etching solution composition consisting of purified water with the following components and balance as shown in Table 1 was prepared.

[0104] Table 1 [Preparation Example 2: Preparation of Etching Solution Composition] An etching solution composition consisting of purified water with the composition and balance shown in Table 2 below was prepared.

[0105] Table 2 [Preparation Example 3: Preparation of Etching Solution Composition] An etching solution composition consisting of purified water with the following components and balance as shown in Table 3 was prepared.

[0106] Table 3

Preparation Example 4: Preparation of Etching Solution Composition

[0107] Table 4 [Experimental Example: Performance Evaluation of Etching Solution Composition] Regulatory factors: In Tables 5 to 8 below, A:F is the weight ratio of amine to fluoride, 4N:3N is the weight ratio of tetrazolium cyclic compound to trizolium cyclic compound, 4N:A is the weight ratio of tetrazolium cyclic compound to amine, and S:P is the weight ratio of sulfate to phosphate.

[0108] Sample manufacturing: A sample substrate with a photoresist pattern is prepared by performing a photolithography process on a substrate on which an amorphous silicon film (thickness: about 1,000 Å), a molybdenum alloy film (thickness: about 400 Å) is deposited, and a copper film (thickness: about 3,000 to 7,000 Å) is formed on the amorphous silicon film.

[0109] The surface and cross-sectional analysis of the etched metal film in the etching process described later will be performed using a SEM (Hitachi product, model SU-8010).

[0110] CD Bias Measurement: After adding Cu powder (1,000 ppm) to the etching solution compositions of each of the preparation examples 1 to 4, the samples were prepared by stirring with a magnetic stirrer at 400 rpm until completely dissolved. For the sample substrates, a wet etching process was performed using the sample solution at approximately 30°C for 70 to 170 seconds.

[0111] On the other hand, CD bias (CD-Bias) represents the distance between the end of the photoresist pattern and the end of the etched copper film. For a small and uniform taper angle, a bias of 0.6 μm or more but less than 0.8 μm on one side is rated as "◎", 0.5 μm or more but less than 0.6 μm or more than 0.8 μm but less than 0.90 μm is rated as "○", and less than 0.5 μm or more than 0.9 μm is rated as "△".

[0112] Based on the change in CD Bias due to changes in copper concentration: After adding Cu powder (1,000 ppm) to the etching solution compositions of each of the preparation examples 1 to 4, a first sample solution was prepared by stirring at 400 rpm using a magnetic stirrer until completely dissolved. For the sample substrate, a wet etching process was performed at approximately 30°C for 70 to 170 seconds using the first sample solution. The distance between the end of the photoresist pattern and the end of the etched copper film is defined as W1.

[0113] After adding Cu powder (7,000 ppm) to the etching solution compositions of each of the preparation examples 1 to 4, a second sample solution was prepared by stirring at 400 rpm using a magnetic stirrer until completely dissolved. For the new sample substrate, a wet etching process was performed at approximately 30°C for 70–170 seconds using the second sample solution. The distance between the end of the photoresist pattern and the end of the etched copper film is defined as W2.

[0114]

Mathematical Formula 1

[0115] The CD deviation (CD Bias) change (△W) calculated according to the mathematical formula 1 is evaluated as "◎" when it is less than 0.2μm, "○" when it is above 0.20μm but below 0.30μm, and "△" when it exceeds 0.30μm.

[0116] Taper angle: For the new sample substrate, etching is performed using the first sample solution. The taper angle represents the angle formed between the lower surface and the side surface of the etched copper film. A taper angle of 55° or more but less than 65° is rated as "◎", 45° or more but less than 55° or more than 65° but less than 70° is rated as "○", and less than 45° or more than 70° or no etching is rated as "△".

[0117] a-Si etching rate: For the new sample substrate, etching was performed using the first sample solution. The etching time (End Point Detection, EPD) of the copper and molybdenum alloy films was measured, and over-etching was performed based on this. The etching rate was measured by observing the cross-section of the etched amorphous silicon film using a scanning electron microscope. A value of 8 Å / sec or higher was rated as "◎", a value between 5 Å / sec and 8 Å / sec was rated as "○", and a value below 5 Å / sec was rated as "△".

[0118] Undercut: Undercutting indicates over-etching in the opposite direction beneath the copper film or molybdenum alloy, and it is the cause of reduced resolution in the etched model. Undercutting is rated as "none" when it is absent and "present" when it is present.

[0119] Residue: Residue is the residue in the form of small protrusions on the surface of the metal film obtained through the etching process. For the etched sample, the absence of molybdenum alloy film residue is evaluated as "none", the presence of residue is evaluated as "present", the absence of etching is evaluated as "not etched", and the absence of dissolution of the molybdenum alloy film in the etching solution composition is evaluated as "dissolved X".

[0120] Thermal stability: Prepare 1 L of each etching solution composition in a 5 L beaker. Add Cu powder (7,000 ppm) to the prepared etching solution composition (30°C) and stir with a magnetic stirrer at 400 rpm until completely dissolved to prepare a solution. Heat the solution with the completely dissolved Cu powder at 25–35°C until boiling, stirring the solution at the process temperature and allowing it to stand. Simultaneously monitor the temperature change of the etching solution composition in real time.

[0121] The thermal stability of the prepared etching solution composition was measured and evaluated by heating for more than 24 hours until it reached boiling point. When the temperature of the etching composition did not change and no heat was generated after more than 24 hours, the thermal stability was evaluated as "stable". When temperature changes and heat generation occurred before 24 hours, the thermal stability was evaluated as "unstable".

[0122] Table 5 Table 6 Table 7 Table 8 Table 9 In the table above, when comparing Examples 1 and 23 with Comparative Examples 21 and 22, Example 1 demonstrates that by adjusting the weight ratio of the tetranitrogen cyclic compound to the trinitrogen cyclic compound to 1:0.01 or more and 1:1.25 or less, the copper film is etched to an appropriate level without residue. Furthermore, when comparing Examples 1 and 23, Example 1, relative to Example 23, reduces the change in critical dimension bias (CD) due to variations in copper concentration in the etching solution composition, and achieves an appropriate taper angle and an appropriate etching rate for the amorphous silicon film by adjusting the weight ratio of the tetranitrogen cyclic compound to the trinitrogen cyclic compound to 1:0.1 or more and less than 1:0.17.

[0123] In the table, when comparing Examples 1 to 3 with Comparative Examples 1 and 2, Examples 1 to 3, which adjust the hydrogen peroxide content relative to 100 parts by weight of the etching solution composition to 5 parts by weight or more to 25 parts by weight or less, compared with Comparative Examples 1 and 2, can reduce the change in Critical Dimension Bias (CD) as the copper concentration in the etching solution composition changes, and show that they achieve an appropriate level of CD bias and an appropriate level of taper angle, an appropriate level of etching rate for amorphous silicon films, and the effect of no undercutting and residue.

[0124] In the table, when comparing Examples 4 and 5 with Comparative Examples 3 and 4, Examples 4 and 5, which adjusted the sulfate content of 100 parts by weight of the etching solution composition to 0.05 parts by weight or more and 2 parts by weight or less, showed an appropriate level of CD deviation and a low amount of CD deviation variation compared with Comparative Examples 3 and 4, and showed the effect of no residue.

[0125] In the table, when comparing Examples 6 and 7 with Comparative Examples 5 and 6, Examples 6 and 7, in which the phosphate content relative to 100 parts by weight of the etching solution composition was adjusted to 0.05 parts by weight or more to 2 parts by weight or less, showed an appropriate level of CD deviation and a low amount of CD deviation variation, and showed the effect of no residue.

[0126] In the table, when comparing Examples 8 and 9 with Comparative Examples 7 and 8, Examples 8 and 9, in which the content of chelating agent relative to 100 parts by weight of the etching solution composition was adjusted to more than 1 part by weight and less than 5 parts by weight, showed an appropriate level of CD deviation while exhibiting excellent thermal stability.

[0127] In the table, when comparing Examples 10 and 11 with Comparative Examples 9 and 10, Examples 10 and 11, in which the content of the diol compound in 100 parts by weight of the etching solution composition was adjusted to more than 1 part by weight and less than 5 parts by weight, showed excellent thermal stability and no residue.

[0128] In the table, when comparing Examples 12 and 13 with Comparative Examples 11 and 12, Examples 12 and 13, in which the amine content relative to 100 parts by weight of the etching solution composition was adjusted to 0.1 parts by weight or more to 1.0 parts by weight or less, showed excellent thermal stability and no residue.

[0129] In the table, when comparing Examples 14 and 15 with Comparative Examples 13 and 14, Examples 14 and 15, in which the content of fluoride relative to 100 parts by weight of the etching solution composition was adjusted to 0.1 parts by weight or more to 1.0 parts by weight or less, achieved an appropriate etching rate of the amorphous silicon film while indicating the absence of residue.

[0130] In the table, when comparing Examples 16 and 17 with Comparative Examples 15 and 16, Examples 16 and 17, in which the content of tetranitrogen cyclic compound relative to 100 parts by weight of the etching solution composition was adjusted to 0.1 parts by weight or more to 1.0 parts by weight or less, showed an appropriate level of CD deviation and a low amount of CD deviation variation, while also showing the effect of no residue.

[0131] In the table, when comparing Examples 18 and 19 with Comparative Examples 17 and 18, Examples 18 and 19, in which the content of the triazine cyclic compound relative to 100 parts by weight of the etching solution composition was adjusted to 0.01 parts by weight or more to 0.5 parts by weight or less, showed an appropriate level of CD deviation and a low amount of CD deviation variation, while also showing no undercutting effect.

[0132] In the table above, when comparing Examples 1 and 22 with Comparative Examples 19 and 20, Examples 1 and 22, where the weight ratio of amine to fluoride relative to 100 parts by weight of the etching solution composition was adjusted to 1:0.1 or higher to 1:3.85 or lower, showed an appropriate level of etching rate for the amorphous silicon film while also exhibiting the effect of no undercutting and residue. Furthermore, when comparing Examples 1 and 22, Example 1, where the ratio was adjusted to 1:0.5 or higher to 1:1 or lower, showed a further improvement in the etching rate performance of the amorphous silicon film compared to Example 22, while also exhibiting a further reduction in the aforementioned CD deviation change.

[0133] In the table, when comparing Examples 1 and 24 with Comparative Examples 23 and 24, by adjusting the weight ratio of the tetranitrogen cyclic compound to the amine to 1:0.1 or more to 1:3.5 or less, specifically 1:0.5 or more to 1:1 or less, it was confirmed that the performance of etching rate of amorphous silicon film was further improved while the CD deviation at an appropriate level and the aforementioned CD deviation change amount were further reduced.

[0134] In the table, when comparing Examples 1 and 25 with Comparative Examples 25 and 26, by adjusting the weight ratio of sulfate to phosphate to 1:1.5 or more to 1:3 or less, specifically 1:2.1 or more to 1:2.8 or less, it was confirmed that the performance of etching rate of amorphous silicon film was further improved while the CD deviation at an appropriate level and the change in CD deviation were further reduced.

[0135] In the table, when comparing Examples 26 and 27, by adjusting the weight ratio of acetate to fluoride to 1:1.5 or higher and 1:3 or lower, a low CD deviation variation, an appropriate taper angle, and an increase in etching rate to an appropriate level for the amorphous silicon film were confirmed.

[0136] Unless otherwise expressly stated, the features described in one embodiment above can be combined with other embodiments. Furthermore, although preferred embodiments of the invention have been described in detail above, the scope of the invention is not limited thereto. Various modifications and improvements made by those skilled in the art using the basic concept of the invention as defined in the claims also fall within the scope of the invention.

Claims

1. An etching solution composition comprising: Hydrogen peroxide; Phosphate; Amines have at least one or more hydroxyl groups; Fluorides; Tetranitrogen cyclic compounds having four nitrogen atoms within the ring; and Trinitrogen cyclic compounds, having three nitrogen atoms within the ring, and The weight ratio of the tetranitrogen cyclic compound to the trinitrogen cyclic compound is greater than 1:0.01 and less than 1:1.

25.

2. The etching solution composition according to claim 1, wherein, The content of hydrogen peroxide is between 5 parts by weight and 25 parts by weight relative to 100 parts by weight of the etching solution composition.

3. The etching solution composition according to claim 1, wherein, The phosphate content is 0.05 parts by weight to 2 parts by weight relative to 100 parts by weight of the etching solution composition.

4. The etching solution composition according to claim 1, wherein, The content of the amine is 0.1 parts by weight to 1.0 parts by weight relative to 100 parts by weight of the etching solution composition.

5. The etching solution composition according to claim 1, wherein, The content of the fluoride is 0.1 parts by weight to less than 1.0 parts by weight relative to 100 parts by weight of the etching solution composition.

6. The etching solution composition according to claim 1, wherein, The content of the tetranitrogen cyclic compound is 0.1 parts by weight to 1.0 parts by weight relative to 100 parts by weight of the etching solution composition.

7. The etching solution composition according to claim 1, wherein, The content of the trinitrogen cyclic compound is 0.01 parts by weight to 0.5 parts by weight relative to 100 parts by weight of the etching solution composition.

8. The etching solution composition according to claim 1, wherein, The weight ratio of the amine to the fluoride is between 1:0.1 and 1:3.85 or less.

9. The etching solution composition according to claim 1, wherein, The weight ratio of the tetrazolium cyclic compound to the amine is greater than 1:0.1 and less than 1:3.

5.

10. The etching solution composition according to claim 1, wherein, The weight ratio of the triazine cyclic compound to the amine is 1:0.5 or more to 1:26 or less.

11. The etching solution composition according to claim 1, further comprising: It is selected from one or more of the group consisting of sulfates, chelating agents having at least one acetate group, and diol compounds.

12. The etching solution composition according to claim 11, wherein, The content of sulfate is 0.05 parts by weight to 2 parts by weight relative to 100 parts by weight of the etching solution composition.

13. The etching solution composition according to claim 11, wherein, The weight ratio of the sulfate to the phosphate is greater than 1:0.05 and less than 1:

30.

14. The etching solution composition according to claim 11, wherein, The content of the chelating agent is more than 1 part by weight and less than 5 parts by weight relative to 100 parts by weight of the etching solution composition.

15. The etching solution composition according to claim 11, wherein, The content of the diol compound is between 1 part by weight and 5 parts by weight relative to 100 parts by weight of the etching solution composition.

16. The etching solution composition according to claim 1, further comprising: The additive is selected from any one of the groups consisting of etching modifiers, surfactants, and combinations thereof.

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