Etching agent composition and etching method using the same

Abstract

An etching solution composition according to one embodiment comprises: an oxidant; an etchant comprising a fluorine (F) compound; and an inhibitor comprising a heterocyclic compound having one or more aromatic ring substituents having 6 to 20 carbon atoms, and the heterocyclic compound comprising one or more of nitrogen (N), sulfur (S), and oxygen (O). An etching method for an etchable film according to one embodiment includes preparing an etchable film comprising a molybdenum (Mo) film and a titanium silicon nitride film; and etching the etchable film using the etching solution composition.

Description

Technical Field

[0001] The following embodiments relate to an etching solution composition and an etching method using the same. Prior Technology

[0002] In recent years, with the rapid development of semiconductor technology, the integration of internal circuits in semiconductor components has made it possible to miniaturize components, and electronic devices containing semiconductor components have become smaller and more portable.

[0003] In semiconductor manufacturing processes, to create miniature semiconductor devices with various functions, it is necessary to introduce two or more thin films with different properties onto a substrate to form complex and highly integrated circuits. For example, various thin films such as silicon oxide, silicon nitride, titanium nitride, and polycrystalline silicon can be introduced into semiconductor processes. These thin films serve as insulating films, barrier films, and stop films in semiconductor processes and devices.

[0004] Semiconductor etching is a process that retains desired films and removes unwanted films based on the characteristics of the semiconductor device being manufactured. This semiconductor etching process requires rapid and accurate removal of the films that need to be removed, while minimizing the impact on other films. Therefore, continuous research is needed on etching compositions and methods that maintain consistent selectivity for specific target films while protecting other films. Summary of the Invention

[0005] [Technical problem to be solved] One embodiment aims to provide an etching solution composition that maintains nearly the same etching rate for molybdenum (Mo) films and titanium silicon nitride (TSN) films, while minimizing etching of other types of films such as atomic layer deposited oxide (ALD) films, silicon nitride (SiN) films, and polycrystalline silicon (Poly Si) films, thereby protecting the target film.

[0006] However, the technical problem to be solved by the present invention is not limited to the topics mentioned above, and other topics not mentioned will be clearly understood by those skilled in the art from the following description. [Technical means to solve the problem]

[0007] An etching solution composition according to one embodiment comprises: an oxidant; an etchant comprising a fluorine (F) compound; and an inhibitor comprising a heterocyclic compound having one or more aromatic ring substituents having 6 to 20 carbon atoms, and the heterocyclic compound comprising one or more of nitrogen (N), sulfur (S), and oxygen (O).

[0008] The oxidant comprises one or more of hydrogen peroxide (H2O2), periodic acid, and peracetic acid. The content of the oxidant may be from 0.001% by weight to 10% by weight relative to the total weight of the etching solution composition.

[0009] The fluorine (F) compound in the etchant comprises one or more of the following: hydrogen fluoride, ammonium fluoride, ammonium bifluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, tetrabutyl fluoride, fluoroboric acid (BF4H), and fluorosilicic acid (H2SiF6). The content of the etchant relative to the total weight of the etching solution composition can be from 0.001% by weight to 5% by weight.

[0010] The aromatic ring substituent having 6 to 20 carbon atoms is one or more of benzene, naphthalene, and anthracene.

[0011] The inhibitors include quinine, pyrilamine maleate salt, sulfapyridine, sulfathiazole, omeprazole, 2-phenyl-2-imidazole, 2-phenyl-2-oxazoline, 3-phenyl-1H-pyrazole, benzylaminopurine, 4-(3-phenylpropyl)piperidine, and 9,10 One or more of the following: bis(4-pyridyl)anthracene, 4-[(E)-2-(9-anthrayl)vinyl]pyridine, 4-(naphthalene-2-yl)-1H-imidazopyridine, 2-phenylfuran, 5-phenyloxazole, 2-phenylthiophene, 2-phenylthiazole, and 1-[(thiazole-2-yl)azo]-2-naphthol. The content of the inhibitor may be from 0.0001% by weight to 5% by weight relative to the total weight of the etching solution composition.

[0012] The etching solution composition according to one embodiment further comprises a pH adjuster, wherein the pH adjuster comprises one or more of hydrochloric acid, sulfuric acid, nitric acid, methansulfonic acid, p-toluenesulfonic acid, oxalic acid, sulfamic acid, monoethanolamine, diethanolamine, triethanolamine, and propanolamine. The content of the pH adjuster relative to the total weight of the etching solution composition is 0.01 to 10% by weight.

[0013] The etching solution composition according to one embodiment further comprises a second inhibitor, the second inhibitor comprising an azole compound. In this case, the content of the second inhibitor relative to the total weight of the etching solution composition is greater than 0% by weight and less than or equal to 5% by weight. The second inhibitor comprises one or more of tolyltriazole, oxadiazole, triazole, tetraazole, isoazole, oxazole, isothiazole, isoxazole, imidazole, pyrrole, pyrazole, thienazole, furazole, and thioxaole.

[0014] The etching solution composition according to one embodiment further comprises an organic solvent, said organic solvent being a polar aprotic solvent or a polar protic solvent, wherein the content of said organic solvent is greater than 0% by weight and less than or equal to 50% by weight relative to the total weight of said etching solution composition. The organic solvents include dimethyl sulfoxide (DMSO), triethylene glycol dimethyl ether (DMTG), acetamide, N-methylpyrrolidone (NMP), piperazine, morpholine, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, polyethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and diethylene glycol diethyl ether. It contains one or more of the following: ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, triethylene glycol methyl butyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, and butyl carbitol.

[0015] The pH value of the etching solution composition according to one embodiment is from 0 to 4.

[0016] The etchable film of the etchant composition according to one embodiment comprises a molybdenum (Mo) film and a titanium silicon nitride film.

[0017] An etching method for an etchable film according to one embodiment includes the step of preparing an etchable film comprising a molybdenum (Mo) film and a titanium silicon nitride (TiSi) film. It also includes the step of etching the etchable film using an etching solution composition. The etching solution composition comprises: an oxidant; an etchant comprising a fluorine (F) compound; and an inhibitor comprising a heterocyclic compound having one or more aromatic ring substituents having 6 to 20 carbon atoms, and the heterocyclic compound comprising one or more of nitrogen (N), sulfur (S), and oxygen (O). [Invention Effects]

[0018] According to one embodiment, the etching solution composition hardly etches the target film, such as atomic layer deposited oxide (ALD) film, silicon nitride (SiN) film, and polycrystalline silicon (Poly Si) film, thereby protecting the target film.

[0019] Furthermore, the composition maintains almost the same etching rate for the molybdenum (Mo) film and the titanium silicon nitride (TSN) film, thereby achieving selective etching of the target film. In addition, the etching ratio of the molybdenum (Mo) target film to the titanium silicon nitride (TSN) film can be maintained at about 0.5:1 to 1:1.

[0020] Furthermore, when patterns are formed on an object film consisting of a molybdenum (Mo) film and a titanium silicon nitride (TSN) film, uniform circuit linewidths can be effectively achieved.

[0021] The effects of this invention are not limited to those described herein, but should be understood to include all effects inferred from the structure of the invention as described in the specification or claims of this invention. Implementation

[0022] The embodiments will now be described in detail with reference to the accompanying drawings. It should be understood that various modifications can be made to the embodiments, and the scope of this invention is not limited to the embodiments described below. All modifications to the embodiments, their equivalents, and even their substitutions are within the scope of this invention.

[0023] The terminology used in this invention is for illustrative purposes only and is not intended to limit the scope. Unless otherwise specified in the text, singular expressions include plural meanings. In this specification, terms such as "comprising" or "having" are used to indicate the presence of the features, numbers, steps, operations, constituent elements, accessories, or combinations thereof described in the specification, and do not exclude the presence of one or more other features, numbers, steps, operations, constituent elements, accessories, or combinations thereof, or additional functions.

[0024] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the common meaning as understood by one skilled in the art. Terms commonly used and identical to dictionary definitions should be understood as having a meaning consistent with the common content of the relevant art, and should not be overly idealized or interpreted as having a formal meaning unless explicitly stated in this case.

[0025] When describing the embodiments with reference to the accompanying drawings, the same constituent elements in each figure are given the same element symbols. In the process of describing the embodiments, when it is determined that a detailed description of a well-known structure or function would cause unnecessary confusion in this case, such detailed description is omitted.

[0026] Furthermore, when describing the constituent elements of the embodiments, terms such as first, second, A, B, (a), and (b) may be used. These terms are only used to distinguish one constituent element from other constituent elements and are not used to limit the nature or order of the corresponding constituent elements. When it is stated that a constituent element is "connected" or "coupled" to another constituent element, it can be directly connected to or attached to the other constituent element; however, it can also be understood that other constituent elements exist therein. Conversely, when it is stated that a constituent element is "directly connected" or "directly coupled" to another constituent element, it can be understood that no other constituent elements exist therein.

[0027] When a constituent element has a common function with a constituent element of a certain embodiment, the same name is used in other embodiments for description. Unless otherwise stated, the description of one embodiment is applicable to other embodiments, and detailed descriptions of repeated content may be omitted.

[0028] The term "about" should be understood as the same range of numbers used by someone of ordinary skill in the art to achieve the same function or result. When the term "about" is used with a number or value, it means ±20%, typically ±10%, typically ±5%, or ±2% of that number or value. In some embodiments, "about" may refer to the number or value itself.

[0029] In this case, expressions such as "A or B", "at least one of A and B", "at least one of A or B", "A, B or C", "at least one of A, B and C", and "at least one of A, B or C" may include all possible combinations of the items listed together. [Etching Solution Composition]

[0030] In one embodiment, the etching solution composition may include an oxidant; an etchant comprising a fluorine (F) compound; and an inhibitor comprising a heterocyclic compound having one or more aromatic ring substituents having 6 to 20 carbon atoms, and the heterocyclic compound comprising one or more of nitrogen (N), sulfur (S), and oxygen (O).

[0031] In one embodiment, the oxidant in the etching solution composition is used to etch specific target films, particularly molybdenum (Mo) films and titanium silicon nitride (TSN) films. For example, the oxidant may contain one or more of hydrogen peroxide (H2O2), periodic acid, and peracetic acid.

[0032] The content of the oxidant can be from 0.001 to 10% by weight of the total weight of the etching solution composition, specifically from 0.005% to 5% by weight, more specifically from 0.005% to 1% by weight, or from 0.005% to 0.05% by weight, or from 0.008% to 0.03% by weight. When the content of the oxidant is within the above range, it can prevent the rapid increase of the metal ion concentration from causing the oxidant to decompose during the required etching period, thereby improving the stability of the etching composition and making it less prone to heat generation and compositional changes. Conversely, when it is below the lower limit of the above range, it may not be possible to ensure a sufficient etching rate; when it is above the upper limit of the above range, it may be difficult to control the etching rate of the metal film and to adjust the selectivity ratio of the molybdenum (Mo) film and titanium silicon nitride (TSN) film to a uniform level.

[0033] In one embodiment, the etchant in the etching solution composition comprises a fluorine (F) compound, which can be used to etch specific target films, particularly molybdenum (Mo) films and titanium silicon nitride (TSN) films, by ionization of fluorine in the fluorine (F) compound.

[0034] The fluorine (F) compound may include one or more of hydrogen fluoride, ammonium fluoride, ammonium bifluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, tetrabutyl fluoride, fluoroboronic acid (BF4H), and fluorosilicic acid (H2SiF6), but the embodiments are not limited thereto. Hydrogen fluoride (HF) or ammonium fluoride (NH4F) is preferred. Hydrogen fluoride (HF) and ammonium fluoride (NH4F) not only ensure excellent etching rates but also offer superior safety.

[0035] The etchant content can be from 0.001% to 5% by weight of the total weight of the etching solution composition, preferably from 0.005% to 3% by weight, more preferably from 0.01% to 2% by weight, and even more preferably from 0.02% to 1% by weight. When the etchant content is below the lower limit of the above range, the etching rate of the titanium silicon nitride (TSN) film will be reduced, making it difficult to control the selectivity; when it exceeds the upper limit of the above range, it may damage the film to be protected (e.g., silicon film, polycrystalline silicon film, oxide film, or silicon nitride film), resulting in pattern defects.

[0036] In one embodiment, the inhibitor in the etching solution composition can suppress the etching of films such as atomic layer deposited oxide (ALD) films, tetraethyl orthosilicate (TEOS) films, silicon nitride films, and polycrystalline silicon films by adjusting the etching rate. This effectively protects films other than molybdenum (Mo) films and titanium silicon nitride (TSN) films.

[0037] The inhibitor may comprise a heterocyclic compound having one or more aromatic ring substituents having 6 to 20 carbon atoms, and the heterocyclic compound comprising one or more of nitrogen (N), sulfur (S), and oxygen (O). The aromatic ring substituents may have 6 to 20 carbon atoms, preferably 6 to 14, and specific examples may be benzene, naphthalene, or anthracene.

[0038] Inhibitors with such aromatic ring substituents can include, for example, quinine, pyrilamine maleate salt, sulfapyridine, sulfathiazole, omeprazole, 2-phenyl-2-imidazole, 2-phenyl-2-oxazoline, 3-phenyl-1H-pyrazole, benzylaminopurine, 4-(3-phenylpropyl)piperidine, 9,10 9,10-Bis(4-pyridyl)anthracene, 4-[(E)-2-(9-anthrayl)vinyl]pyridine, 4-(naphthalene-2-yl)-1H-imidazopyridine, 2-phenylfuran, 5-phenyloxazolium The formulation may contain one or more of the following: ole), 2-phenylthiophene, 2-phenylthiazole, and 1-[(thiazole-2-yl)azo]-2-naphthol, but the implementation is not limited thereto. Preferably, it may contain benzylaminopurine, sulfapyridine, 3-phenyl-1H-pyrazole, 2-phenylthiophene, 2-phenylthiazole, 1-[(thiazole-2-yl)azo]-2-naphthol, and / or 2-phenylfuran.

[0039] The content of the inhibitor can be from 0.0001% to 5% by weight of the total weight of the etching solution composition, preferably from 0.01% to 3% by weight, more preferably from 0.1% to 2% by weight, and even more preferably from 0.3% to 1.5% by weight. When the content of the inhibitor is within the above range, it can prevent the etching solution composition from becoming unstable during the etching process due to the decomposition reaction of the oxidant and the etchant. When it is below the lower limit of the above range, it will significantly reduce the etching rate of the metal film and may not be able to exert a sufficient inhibitory effect. When it exceeds the upper limit of the above range, it may cause precipitation due to excessive solubility.

[0040] As mentioned above, the etching solution composition according to one embodiment, by simultaneously containing a certain amount of a specific etchant and a specific inhibitor, can ensure that the etching rates for molybdenum (Mo) films and titanium silicon nitride (TSN) films are at similar levels.

[0041] The etching solution composition according to one embodiment may further include a pH adjuster, and the pH value of the etching solution composition can be adjusted to an appropriate level using the following amounts of the pH adjuster. Specifically, the pH adjuster may be one or more of hydrochloric acid, sulfuric acid, nitric acid, methansulfonic acid, p-toluenesulfonic acid, oxalic acid, sulfamic acid, monoethanolamine, diethanolamine, triethanolamine, and propanolamine. The content of the pH adjuster may be from 0.01% to 10% by weight of the total weight of the etching solution composition, specifically from 0.1% to 7% by weight, more specifically from 0.5% to 5% by weight, and even more specifically from 1% to 4% by weight. An appropriate amount of this pH adjuster can be used to adjust the pH value of the etching solution composition to the desired pH range.

[0042] Furthermore, when the etching solution composition according to one embodiment contains the pH adjuster as described above, the pH value of the etching solution composition can be from 0 to 4, preferably from 0.5 to 2. When the pH value exceeds the above range, the etching reaction of fluorine compounds may not proceed normally, reducing the protective effect of the inhibitor on atomic layer deposited oxide (ALD) films, tetraethyl orthosilicate (TEOS) films, silicon nitride films, and polycrystalline silicon films.

[0043] The etching solution composition according to one embodiment may further contain a second inhibitor.

[0044] This second inhibitor, together with the aforementioned inhibitors, protects the target film from etchants and oxidants, including those containing fluorine (F) compounds, and this function can be achieved using azole compounds. When azole compounds are used, not only can the etching rate of the metal film be slightly reduced, but a stable etching rate can also be maintained even when the etching process time is extended. Specific types of the second inhibitor include one or more of the following: tolyltriazole, oxadiazole, triazole, tetraazole, isoazole, oxazole, isothiazole, isoxazole, imidazole, pyrrole, pyrazole, thienazole, furazole, and thioxaole.

[0045] The second inhibitor is a component that may be further included in the etching solution composition, and its content may be from 0% to 5% by weight of the total weight of the etching solution composition. Specifically, its content may be greater than 0% by weight and less than or equal to 3% by weight, and more specifically, it may be greater than 0% by weight and less than or equal to 2% by weight.

[0046] The etching solution composition according to one embodiment may also contain an organic solvent. The organic solvent includes polar aprotic solvents or polar protic solvents. Specific examples of the organic solvent include dimethyl sulfoxide (DMSO), triethylene glycol dimethyl ether (DMTG), acetamide, N-methylpyrrolidone (NMP), piperazine, morpholine, ethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, polyethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. The ether is one or more of the following: diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, triethylene glycol methyl butyl ether, propylene glycol dimethyl ether, and dipropylene glycol dimethyl ether, preferably butyl carbitol.

[0047] The organic solvent is a component that may be further included in the etching solution composition, and its content may be from 0% to 50% of the total weight of the etching solution composition, specifically greater than 0 and less than or equal to 50% by weight, more specifically from 5% to 30% by weight, and even more specifically from 10% to 20% by weight.

[0048] In the etching solution composition according to one embodiment, although not explicitly mentioned, water may constitute 100% of the remaining portion by weight of all components other than water, relative to the total etching solution. The water used in the etching solution of the present invention is preferably semiconductor-grade water or ultrapure water.

[0049] According to one embodiment, the etching solution composition can be used to etch an object film including a molybdenum (Mo) film and a titanium silicon nitride (TSN) film.

[0050] In one embodiment, the etching rate of the etching solution composition for the molybdenum (Mo) film can be from 5 Å / min to 20 Å / min, and the etching rate for the titanium silicon nitride (TSN) film can be from 5 Å / min to 20 Å / min. Furthermore, the etching rate ratio of the molybdenum (Mo) film to the titanium silicon nitride film can be from 0.5 to 1:1.

[0051] Furthermore, the etching rate of the silicon oxide film, atomic layer deposited oxide (ALD) film, silicon nitride film, or polycrystalline silicon film can be below 1 Å / min. [Etching Method]

[0052] The etching solution composition according to one embodiment can be used to etch a target film comprising a molybdenum (Mo) film and a titanium nitride silicon film. The etching method for the target film includes the following steps: preparing a target film comprising a molybdenum (Mo) film and a titanium nitride silicon film; and The etching solution composition is used to etch the film to be etched. At this point, the etching solution composition is substantially the same as the etching solution composition described in detail above, and will not be repeated hereafter.

[0053] Using the above etching method, at an etching process temperature of about 50°C to 70°C, the etching rate for molybdenum (Mo) and titanium nitride silicon (TSN) films is about 5 to 20 Å / min, while the etching rate for atomic layer oxide films, silicon nitride films and polycrystalline silicon films can reach less than 1 Å / min.

[0054] The present invention will now be described in more detail through embodiments. These embodiments are for illustrative purposes only, and the scope of the invention is not limited thereto. [Example] 1) Preparation method: Preparation of etching solution composition

[0055] The etching solutions of Examples 1 to 17 and Comparative Examples 1 to 13 were prepared according to the composition in Table 1 below.

[0056] The preparation methods of Examples 6 and 7 are the same as those of Example 1, except that 0.42% by weight of tolyltriazole and 0.3% by weight of imidazole are added as second inhibitors, respectively. [Table 1] Composition (wt%) Oxidizing agent Etching agent Inhibitors pH adjuster Second inhibitor DIW pH Comparative Example 1 periodic acid HF - - - Balance 4.1 0.01 0.025 - - - Comparative Example 2 periodic acid HF - Methylsulfonic acid - margin 0.8 0.01 0.025 - 2 - Comparative Example 3 periodic acid HF - Methylsulfonic acid - margin 1.1 0.01 0.025 - 1 - Comparative Example 4 periodic acid HF - Methylsulfonic acid - margin 0.5 0.01 0.025 - 5 - Comparative Example 5 periodic acid HF - Phosphoric acid - margin 0.7 0.01 0.025 - 10 - Comparative Example 6 periodic acid NH4F - Methylsulfonic acid - margin 1 0.01 0.045 - 2 - Comparative Example 7 periodic acid NH4F - Methylsulfonic acid - margin 0.5 0.01 0.045 - 5 - Comparative Example 8 periodic acid NH4F 4-Methylpyridine Methylsulfonic acid - margin 0.9 0.01 0.045 1 2 - Comparative Example 9 periodic acid HF 4-Methylpyridine Methylsulfonic acid - margin 0.9 0.01 0.025 1 2 - Comparative Example 10 periodic acid NH4F 4-Methylpurine Methylsulfonic acid - margin 0.9 0.01 0.045 1.1 2 - Comparative Example 11 periodic acid HF 4-Methylpurine Methylsulfonic acid - margin 0.9 0.01 0.025 1.1 2 - Comparative Example 12 H2O2 HF - Methylsulfonic acid - margin 1 0.1 0.025 - 2 - Comparative Example 13 peracetic acid HF - Methylsulfonic acid - margin 1.2 0.2 0.025 - 2 - Example 1 periodic acid HF benzylaminopurine Methylsulfonic acid - margin 0.9 0.01 0.025 1.35 2 - Example 2 periodic acid NH4F benzylaminopurine Methylsulfonic acid - margin 0.9 0.01 0.045 1.35 2 - Example 3 periodic acid HF sulfapyridine Methylsulfonic acid - margin 0.8 0.01 0.025 0.5 2 - Example 4 periodic acid NH4F sulfapyridine Methylsulfonic acid - margin 0.9 0.01 0.06 0.5 2 - Example 5 periodic acid HF 3-Phenylon-1H-pyrazole Methylsulfonic acid - margin 0.85 0.01 0.025 0.6 2 - Example 6 periodic acid HF benzylaminopurine Methylsulfonic acid Methylbenzotriazole margin 0.6 0.01 0.025 1.35 2 0.42 Example 7 periodic acid HF benzylaminopurine Methylsulfonic acid imidazole margin 0.6 0.01 0.025 1.35 2 0.3 Example 8 periodic acid NH4F benzylaminopurine Methylsulfonic acid - margin 0.9 0.01 0.06 1.35 2 - Example 9 periodic acid HF 2-Phenylenol Methylsulfonic acid - margin 1.0 0.01 0.025 0.6 2 - Example 10 periodic acid NH4F 2-Phenylenol Methylsulfonic acid - margin 1.0 0.01 0.045 0.6 2 - Example 11 H2O2 NH4F benzylaminopurine Methylsulfonic acid - margin 1.1 0.01 0.045 0.8 2 - Example 12 periodic acid NH4F benzylaminopurine Methylsulfonic acid - margin 1 0.01 0.045 0.5 2 - Example 13 periodic acid HF 1-[(thiazolyl-2-yl)azo]-2-naphthol Methylsulfonic acid - margin 0.6 0.01 0.05 0.5 3.5 - Example 14 periodic acid NH4F 1-[(thiazolyl-2-yl)azo]-2-naphthol Methylsulfonic acid - margin 0.7 0.01 0.07 0.5 3.5 - Example 15 periodic acid HF 1-[(thiazolyl-2-yl)azo]-2-naphthol Methylsulfonic acid - margin 0.7 0.01 0.05 0.5 3.5 - Example 16 periodic acid HF 2-Phenylenol Methylsulfonic acid - margin 0.7 0.01 0.025 1.1 3 - Example 17 periodic acid NH4F 2-Phenylenol Methylsulfonic acid - margin 0.7 0.01 0.045 1.1 3 - 2) Experimental Example (Evaluation Method): Evaluating the etching rate of the etching solution composition.

[0057] Test coupons were prepared by cutting TEOS, SiN, TSN, and Mo samples into 2×2 cm pieces. The pre-etching film thickness of the test coupons was measured using a FilmMetrix and a 4-point probe. The etching solution compositions of Comparative Examples 1 to 13 and Examples 1 to 17 were heated to 60°C, and the test coupons were immersed in the etching solution compositions for 1 to 10 minutes. The coupons were then removed and rinsed with running deionized water (DIW) for 30 seconds. The test coupons were then dried with N2 gas, and the post-etching film thickness was measured using a FilmMetrix.

[0058] The etching rate is calculated using the following formula, and the etching rate and selection are shown in Table 2. Etching rate = [film thickness before etching - film thickness after etching] / processing time [Table 2] Etching rate [Å / min] Mo TSN TEOS SiN Polycrystalline silicon (Poly Si) Comparative Example 1 30.3 0.8 0.5 0.4 0.4 Comparative Example 2 214 18.8 0.5 0.4 0.4 Comparative Example 3 168.5 12.6 0.3 0.5 0.5 Comparative Example 4 128.5 12.6 0.6 0.8 0.8 Comparative Example 5 65.3 2.6 0.2 0.4 0.4 Comparative Example 6 113.5 12.66 1 0.6 0.6 Comparative Example 7 122.2 15.1 0.8 0.4 0.4 Comparative Example 8 88.1 14.4 0.7 0.5 0.6 Comparative Example 9 76.3 12.2 0.6 0.8 1 Comparative Example 10 81.2 13.2 1 0.4 0.6 Comparative Example 11 73.8 12.5 1.1 0.6 0.5 Comparative Example 12 130.5 8.4 1 0.8 0.6 Comparative Example 13 80.6 6.2 0.8 0.4 0.6 Example 1 12.5 11.3 0.1 0.2 0.2 Example 2 11.8 11.6 0.2 0.1 0.2 Example 3 9.8 10.2 0.2 0.1 0.1 Example 4 14.2 15.3 0.1 0.08 0.3 Example 5 8.6 9.2 0.2 0.3 0.3 Example 6 10.1 9.8 0.05 0.1 0.1 Example 7 8.2 9.3 0.2 0.3 0.1 Example 8 17.2 16.8 0.2 0.2 0.1 Example 9 10.3 9.8 0.2 0.1 0.05 Example 10 11.2 10.9 0.05 0.2 0.04 Example 11 7 6.7 0.2 0.05 0.1 Example 12 4.3 4.8 0.1 0.1 0.1 Example 13 13.2 14 0.3 0.05 0.2 Example 14 14.3 15 0.1 0.2 0.04 Example 15 13.2 14.8 0.1 0.05 0.1 Example 16 9.8 10.1 0.1 0.2 0.15 Example 17 9.4 9.8 0.15 0.2 0.2

[0059] Observing the etching rates shown in Table 2 for the etching solution compositions in Table 1 above, the results confirm that the etching solution compositions of Examples 1 to 17 exhibit a near-1:1 equilibrium selectivity ratio for Mo and TSN target films compared to Comparative Examples 1 to 7, 12 to 13, and Comparative Examples 8 to 11, while showing lower etching rates for other TEOS films, SiN films, and polysilicon (Poly Si) films. The etching solution compositions of Examples 1 to 17 contain inhibitors of heterocyclic compounds having one or more aromatic ring substituents with 6 to 20 carbon atoms (bonded to benzene, naphthalene, or anthracene), and the heterocyclic compounds contain one or more of nitrogen (N), sulfur (S), and oxygen (O). Comparative Examples 1 to 7 and 12 to 13 do not contain inhibitors, and the heterocyclic compounds in Comparative Examples 8 to 11 do not contain one or more aromatic ring substituents with 6 to 20 carbon atoms (not bonded to benzene, naphthalene, or anthracene), but only contain one or more of nitrogen (N), sulfur (S), and oxygen (O).

[0060] The etching solution composition contains the heterocyclic compound having one or more aromatic ring substituents with 6 to 20 carbon atoms (bonded to benzene, naphthalene, or anthracene) and comprising one or more of nitrogen (N), sulfur (S), and oxygen (O). This etching solution composition exhibits higher selectivity for molybdenum (Mo) films and titanium silicon nitride (TSN) films compared to TEOS films, SiN films, and polycrystalline silicon films. Furthermore, its etching selectivity ratio for molybdenum (Mo) films and titanium silicon nitride (TSN) films is substantially the same (approximately 1:1), which allows for rapid and accurate removal of the target film while minimizing the impact on other films. Moreover, specifically in semiconductor etching processes, this etching solution composition is particularly suitable for creating metal gate recesses in films where titanium silicon nitride (TSN) films are stacked as metal barrier layers and molybdenum (Mo) films are stacked as word line metals.

[0061] In summary, embodiments have been described with reference to the limited accompanying drawings. Those skilled in the art can make various modifications and variations based on this description. For example, appropriate results can be obtained by performing the described techniques in a different order than the described methods, and / or by combining or integrating the described systems, structures, devices, circuits, and other constituent elements in a different manner than the described methods, or by replacing or substituting them with other constituent elements or equivalents.

[0062] Therefore, other embodiments, other implementations, and equivalents of the claims are all within the scope of the claims of this invention.

[0063] none

[0064] Domestic storage information (please note in order of storage institution, date, and number) none

[0065] Overseas storage information (please note in the order of storage country, institution, date, and number) none

Claims

1. An etching solution composition comprising: an oxidant; an etchant comprising a fluorine (F) compound; and an inhibitor comprising a heterocyclic compound having one or more aromatic ring substituents having 6 to 20 carbon atoms, and the heterocyclic compound comprising one or more of nitrogen (N), sulfur (S), and oxygen (O), wherein the etched film of the etching solution composition comprises a molybdenum (Mo) film and a titanium silicon nitride (TSN) film.

2. The etching solution composition of claim 1, wherein the oxidant comprises one or more of hydrogen peroxide (H2O2), periodic acid, and peracetic acid.

3. The etching composition of claim 1, wherein the fluorine (F) compound comprises one or more of hydrogen fluoride, ammonium fluoride, ammonium hydrogen fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, tetrabutyl fluoride, fluoroboric acid (BF4H), and fluorosilicic acid (H2SiF6).

4. The etching composition of claim 1, wherein the aromatic ring substituent having 6 to 20 carbon atoms is one or more of benzene, naphthalene, and anthracene.

5. The etching composition of claim 1, wherein the inhibitor comprises one or more of quinine, pyramine maleate, sulfapyridine, sulfathiazole, omeprazole, 2-phenyl-2-imidazolium, 2-phenyl-2-oxazoline, 3-phenyl-1H-pyrazole, benzylaminopurine, 4-(3-phenylpropyl)piperidine, 9,10-bis(4-pyridyl)anthracene, 4-[(E)-2-(9-anthrayl)vinyl]pyridine, 4-(naphthyl-2-yl)-1H-imidazopyridine, 2-phenylfuran, 5-phenyloxazole, 2-phenylthiophene, 2-phenylthiazole, and 1-[(thiazo-2-yl)azo]-2-naphthol.

6. The etching solution composition of claim 1, further comprising a pH adjuster, said pH adjuster comprising one or more of hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, p-toluenesulfonic acid, oxalic acid, aminosulfonic acid, monoethanolamine, diethanolamine, triethanolamine and propanolamine.

7. The etching solution composition of claim 1, further comprising a second inhibitor comprising an azole compound, wherein the content of the second inhibitor is greater than 0% by weight and less than or equal to 5% by weight relative to the total weight of the etching solution composition.

8. The etching composition of claim 7, wherein the second inhibitor comprises one or more of tolyltriazole, oxadiazole, triazole, tetraazole, isoazole, oxazole, isothiazole, isoxazole, imidazole, pyrrole, pyrazole, thienazole, furazole, and thioxaole.

9. The etching solution composition of claim 1, further comprising an organic solvent, said organic solvent comprising a polar aprotic solvent or a polar protic solvent, wherein the content of said organic solvent is greater than 0% by weight and less than or equal to 50% by weight relative to the total weight of said etching solution composition.

10. The etching composition of claim 9, wherein the organic solvent comprises one or more of dimethyl sulfoxide (DMSO), triethylene glycol dimethyl ether (DMTG), acetamide, N-methylpyrrolidone (NMP), piperazine, morpholine, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, polyethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, triethylene glycol methyl butyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, and butylcarbidol.

11. The etching solution composition of claim 1, wherein the content of the oxidant is from 0.001% by weight to 10% by weight relative to the total weight of the etching solution composition.

12. The etchant composition of claim 1, wherein the content of the etchant is from 0.001% to 5% by weight relative to the total weight of the etchant composition, and the content of the inhibitor is from 0.0001% to 5% by weight relative to the total weight of the etchant composition.

13. The etching solution composition of claim 6, wherein the content of the pH adjuster is 0.01 to 10% by weight relative to the total weight of the etching solution composition, and the pH value of the etching solution composition is 0 to 4.

14. An etching method for etching a target film, comprising the following steps: Prepare an etchable film containing a molybdenum (Mo) film and a titanium nitride silicon film; The etching solution composition of claim 1 is used to etch the film of the object to be etched.