Compositions, methods for treating metal-containing films, and methods for manufacturing electronic devices

Abstract

The invention provides a composition, a method of treating a metal-containing film using the composition, and a method of manufacturing an electronic device using the composition, the composition comprising an oxidant, an acid, and an etching control agent. The etching control agent may comprise at least one of the following: a compound represented by Formula 1 and a polymer comprising repeating units represented by Formula 2, as described in this specification.

Description

[0001] Cross-reference to related applications

[0002] This application is based on and claims priority to Korean Patent Application No. 10-2024-0199346 filed on December 27, 2024, and Korean Patent Application No. 10-2025-0200538 filed on December 16, 2025, the disclosures of which are incorporated herein by reference in their entirety. Technical Field

[0003] This disclosure relates to compositions, methods of treating metal-containing films using the compositions, and methods of manufacturing electronic devices using the compositions. Background Technology

[0004] To meet consumer demand for superior performance and affordable prices, increased integration and improved reliability in semiconductor devices are advantageous. As the integration level of semiconductor devices increases, damage to components during the manufacturing process can have a greater impact on the reliability and electrical characteristics of semiconductor memory devices. Specifically, during semiconductor device manufacturing, a variety of processing techniques, such as etching, cleaning, and polishing, can be applied to a given film (e.g., a metal-containing film), and a composition with an appropriate etching rate can be advantageous for more efficient processing of metal-containing films. Summary of the Invention

[0005] The invention provides compositions capable of more effectively controlling the etching rate of various metal-containing films, methods for treating metal-containing films using the compositions, and methods for manufacturing electronic devices using the compositions.

[0006] Other aspects will be set forth in part in the description which follows, and in part will be apparent from the description or may be learned through practice of the embodiments of this disclosure presented.

[0007] According to one aspect of this disclosure, the composition may include

[0008] Oxidizing agents, acids, and etching control agents, among which

[0009] Etching control agents may include at least one of the following: a compound represented by Formula 1 and a polymer comprising repeating units represented by Formula 2.

[0010] Formula 1

[0011]

[0012] Formula 2

[0013]

[0014] Among them, in equations 1 and 2,

[0015] R1 and R2 can be independently...

[0016] Hydrogen, halogen atoms, -OH、 -SH or -C(=O)OH,

[0017] Each of the following C1-C that was not replaced or was replaced by: 30 Alkyl, C2-C 30 alkenyl, C1-C 30 Alkoxy, C1-C 30 Alkylthio, C3-C 30 Carbocyclic groups or C1-C 30 Heterocyclic groups: halogen atoms, -OH、 -SH、 -C(=O)OH, Cl-C 30 Alkyl, C2-C 30 alkenyl, C1-C 30 Alkoxy, C1-C 30 Alkylthio or any combination thereof, or

[0018] -N(R 13 (R) 14 ),

[0019] R 11 To R 14 Each can be independently

[0020] Hydrogen, halogen atoms, -OH、 -SH or -C(=O)OH, or

[0021] Each of the following C1-C that was not replaced or was replaced by: 30 Alkyl, C2-C 30 alkenyl, C1-C 30 Alkoxy, C1-C 30 Alkylthio, C3-C 30 Carbocyclic groups or C1-C 30 Heterocyclic groups: halogen atoms, -OH、 -SH、 -C(=O)OH, Cl-C 30 Alkyl, C2-C 30 alkenyl, C1-C 30 Alkoxy, C1-C 30alkylthio groups or any combination thereof,

[0022] L1 to L3 can each be independently...

[0023] Single key, O or S, or

[0024] Each of the following C1-C that was not replaced or was replaced by: 30 Alkylene, C2-C 30 alkenyl, C3-C 30 Carbocyclic groups or C1-C 30 Heterocyclic groups: halogen atoms, -OH、 -SH、 -C(=O)OH, Cl-C 30 Alkyl, C2-C 30 alkenyl, C1-C 30 Alkoxy, C1-C 30 alkylthio groups or any combination thereof,

[0025] a1 to a3 can each be an integer from 1 to 30 independently, and

[0026] and Each represents a binding site with an adjacent atom.

[0027] According to another aspect of this disclosure, a method for processing a metal-containing film may include...

[0028] Prepare a substrate (substrate) comprising a metal-containing film, the metal-containing film including a first region and a second region; and

[0029] The metal-containing film is brought into contact with the composition;

[0030] The first and second regions may independently include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), cobalt (Co), copper (Cu), or any combination thereof.

[0031] This includes the fact that the material in the first region may differ from the material included in the second region.

[0032] According to another aspect of this disclosure, a method for manufacturing an electronic device including a transistor is provided. The transistor may include a channel; source and drain electrodes spaced apart from each other and electrically connected to the channel; a gate electrode; and a gate insulating film between the gate electrode and the channel. The method may include:

[0033] Provides a barrier layer including metal nitrides, metal oxynitrides, or any combination thereof;

[0034] Provides a conductive layer comprising a conductive metal; and

[0035] A gate electrode is formed by contacting the barrier layer and the conductive layer with the composition to etch a portion of the barrier layer and a portion of the conductive layer. Attached Figure Description

[0036] The above and other aspects, features, and advantages of some embodiments of this disclosure will become more apparent from the following description taken in conjunction with the accompanying drawings, wherein:

[0037] Figure 1A and 2 This is a schematic diagram illustrating a method for processing metal-containing films.

[0038] Figure 1B It indicates that it can contact composition 30. Figure 1A A schematic diagram of the surface of the metal-containing film 20A;

[0039] Figure 3 and 4 This is a schematic diagram briefly illustrating other embodiments of the method for processing metal-containing films;

[0040] Figure 5 It is a schematic plan view of the electronic device according to the embodiment;

[0041] Figure 6A yes Figure 5 A perspective view of one embodiment of the electronic device shown;

[0042] Figure 6B yes Figure 5 A perspective view of another embodiment of the electronic device shown;

[0043] Figures 7 to 9 It is a brief description of the manufacturing process. Figure 6A A schematic diagram of a portion of the process of the transistor structure shown; and

[0044] Figure 10 This is a process flow diagram illustrating the implementation of a method for manufacturing electronic devices. Detailed Implementation

[0045] The embodiments will now be described in detail, examples of which are illustrated in the accompanying drawings. Throughout the description, the same reference numerals refer to the same elements. In this respect, the embodiments may take different forms and should not be construed as limited to the description set forth herein. Therefore, the embodiments are described below only with reference to the accompanying drawings to illustrate aspects. As used herein, the term “and / or” includes any and all combinations of one or more of the associated enumerated items. Expressions such as “at least one of” modify the entire list of elements and not individual elements of the list when preceding or following it. For example, “at least one of A, B, and C” and similar language (e.g., “at least one selected from A, B, and C” and “at least one of A, B, or C”) can be interpreted as only A, only B, only C, or any combination of two or more of A, B, and C, such as ABC, AB, BC, and AC.

[0046] When the terms “about” or “substantially” are used in conjunction with numerical values ​​in this specification, it is intended that the relevant numerical value includes manufacturing or operational tolerances (e.g., ±10%) around the stated numerical value. Furthermore, when the terms “generally” and “substantially” are used in conjunction with geometry, it is intended that precision of the geometry is not required, but tolerance for the shape is within the scope of this disclosure. Additionally, regardless of whether a numerical value or shape is modified to “about” or “substantially”, it will be understood that these values ​​and shapes should be interpreted as including manufacturing or operational tolerances (e.g., ±10%) around the stated numerical value or shape. When a range is specified, the range includes all values ​​within that range, for example, increments of 0.1%.

[0047] Metal-containing membranes

[0048] Metal-containing films may include alkali metals (e.g., sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), etc.), alkaline earth metals (e.g., beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), etc.), lanthanides (e.g., lanthanum (La), europium (Eu), terbium (Tb), ytterbium (Yb), etc.), and transition metals (e.g., scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf)). Vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), nickel (Ni), copper (Cu), silver (Ag), zinc (Zn), etc.), later transition metals (e.g., aluminum (Al), gallium (Ga), indium (In), thallium (Tl), tin (Sn), bismuth (Bi), etc.), or any combination thereof.

[0049] According to embodiments, the metal-containing film may include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), cobalt (Co), copper (Cu), or any combination thereof.

[0050] According to another embodiment, the metal-containing film may include two or more different types of metals.

[0051] According to another embodiment, the metal-containing film may include titanium.

[0052] According to another embodiment, the metal-containing film may i) include titanium (Ti), and ii) optionally further include indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), silicon (Si), or any combination thereof, in addition to titanium.

[0053] Metal-containing films may include metals, metal nitrides, metal oxides, metal oxynitrides, or any combination thereof.

[0054] According to embodiments, the metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof, and the metal, the metal of the metal nitride, the metal of the metal oxide, and the metal of the metal oxynitride may each include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), cobalt (Co), copper (Cu), or any combination thereof.

[0055] According to another embodiment, the metal-containing film may include metal nitrides, metal oxynitrides, or any combination thereof as described above (e.g., titanium nitrides, titanium oxynitrides, or any combination thereof).

[0056] According to another embodiment, the metal-containing film may include the metals described above (e.g., conductive metals such as tungsten, molybdenum, and ruthenium).

[0057] According to another embodiment, the metal-containing film may include i) metal nitrides, metal oxynitrides or any combination thereof as described above (e.g., titanium nitrides, titanium oxynitrides or any combination thereof, etc.) and ii) metals as described above (e.g., conductive metals such as tungsten, molybdenum and ruthenium).

[0058] According to another embodiment, the metal-containing film may include titanium nitride (titanium nitride), titanium oxynitride (titanium oxynitride), or any combination thereof, and may further include tungsten, molybdenum, ruthenium, or any combination thereof in addition to titanium nitride (titanium nitride), titanium oxynitride (titanium oxynitride), or any combination thereof. Titanium nitride and titanium oxynitride may each optionally further include indium, aluminum, lanthanum, scandium, gallium, silicon, or any combination thereof.

[0059] According to another embodiment, the metal-containing film may include titanium nitride, further including aluminum titanium nitride (e.g., TiAlN), further including lanthanum titanium nitride, further including silicon titanium nitride (e.g., TiSiN), etc.

[0060] Metal-containing films can be single-layer structures comprising one or more types of materials, or multi-layer structures comprising different materials. Multiple films included in a multi-layer structure can be stacked vertically or arranged horizontally relative to a substrate. Single-layer and multi-layer structures can have various three-dimensional patterns (e.g., vias, trenches, etc.).

[0061] According to an embodiment, the metal-containing film includes a first region and a second region, wherein the first region and the second region may independently include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), cobalt (Co), copper (Cu), or any combination thereof, and the material included in the first region may be different from the material included in the second region.

[0062] According to another embodiment, the first region may include titanium.

[0063] According to another embodiment, the first region may i) include titanium (Ti), and ii) optionally further include indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), silicon (Si), or any combination thereof, in addition to titanium.

[0064] According to another embodiment, the second region may include tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

[0065] According to another embodiment, the first region may include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), or any combination thereof, and the second region may include tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

[0066] According to another embodiment, the first region may include a metal nitride, a metal oxynitride, or any combination thereof, and the second region may include a conductive metal.

[0067] For example, the first region may have i) a single-layer structure of a metal nitride film, ii) a single-layer structure of a metal oxynitride film, or iii) a double-layer structure of a metal nitride film and a metal oxynitride film.

[0068] According to another embodiment, the first region may include titanium nitride, titanium oxynitride, or any combination thereof, wherein the titanium nitride and titanium oxynitride may optionally further include indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

[0069] According to another embodiment, the first region may include titanium nitride, further including aluminum titanium nitride (e.g., TiAlN), further including lanthanum titanium nitride, further including silicon titanium nitride (e.g., TiSiN), etc.

[0070] As used herein, etching of any membrane can refer to the removal of at least a portion of the material constituting the membrane.

[0071] Composition

[0072] The composition may include oxidants, acids, and etching control agents.

[0073] The composition can be used in various processing techniques for metal-containing films as described herein, such as etching, cleaning, and polishing processes.

[0074] The composition may further include water.

[0075] According to embodiments, the composition may be substantially free of fluorine-containing compounds. While not intended to be limited by specific theory, when the composition includes a fluorine-containing compound and is used to treat metal-containing films, adjacent materials disposed adjacent to the metal-containing film, such as various oxides, can be damaged, leading to degradation of the performance of electronic and / or semiconductor devices, as described below. In some embodiments, the composition may include a fluorine-containing compound, and the amount of the fluorine-containing compound may be an amount that does not substantially affect the fundamental properties of the composition (e.g., about 10% by weight of the composition). -2 % or less by weight, approximately 10 -3 % or less by weight, approximately 10 -4 % or less by weight, approximately 10 -7 weight% to about 10 -2 % by weight, approximately 10 -6 weight% to about 10 -2 % by weight, approximately 10 -5 weight% to about 10 -2 % by weight, approximately 10 -7 weight% to about 10 -3% by weight, approximately 10 -6 weight% to about 10 -3 % by weight, or about 10 -5 weight% to about 10 -3 (by weight, etc.). In some embodiments, the composition may not include fluorinated compounds. For example, the amount of fluorinated compounds in the composition may be 0% by weight. Fluorinated compounds refer to any compound that contains F and is dissociable in an aqueous solvent, and examples include HF, NH4F, etc.

[0076] According to an embodiment, the composition may include an oxidant, an acid, an etching control agent, and water.

[0077] Oxidizing agent

[0078] The oxidant can etch at least a portion of the metal-containing film and may include hydrogen peroxide, iodine-containing compounds, nitric acid, ammonium sulfate, or combinations thereof.

[0079] In one embodiment, the oxidant may include hydrogen peroxide, periodic acid, iodic acid, nitric acid, ammonium sulfate, or any combination thereof.

[0080] In another embodiment, the oxidant may include hydrogen peroxide.

[0081] In some implementations, the oxidant may be hydrogen peroxide.

[0082] In some embodiments, the composition may substantially exclude fluorine-containing compounds as oxidants. While not intended to be limited by specific theory, when the composition includes fluorine-containing compounds as oxidants and is used to treat metal-containing films, adjacent materials disposed adjacent to the metal-containing film, such as various oxides, can be damaged, leading to degradation of the performance of electronic and / or semiconductor devices.

[0083] Based on 100% by weight of the composition, the amount (by weight) of the oxidant can be, for example, from about 0.001% by weight to about 10% by weight, from about 0.001% by weight to about 7% by weight, from about 0.001% by weight to about 5% by weight, from about 0.001% by weight to about 3% by weight, from about 0.001% by weight to about 1% by weight, from about 0.001% by weight to about 0.7% by weight, from about 0.001% by weight to about 0.5% by weight, from about 0.005% by weight to about 10% by weight, from about 0.005% by weight to about 7% by weight. About 0.005 wt% to about 5 wt%, about 0.005 wt% to about 3 wt%, about 0.005 wt% to about 1 wt%, about 0.005 wt% to about 0.7 wt%, about 0.005 wt% to about 0.5 wt%, about 0.01 wt% to about 10 wt%, about 0.01 wt% to about 7 wt%, about 0.01 wt% to about 5 wt%, about 0.01 wt% to about 3 wt%, about 0.01 wt% to about 1 wt%, about 0.01 wt% to about 0.7 wt%, about 0.0 1 wt% to about 0.5 wt%, about 0.05 wt% to about 10 wt%, about 0.05 wt% to about 7 wt%, about 0.05 wt% to about 5 wt%, about 0.05 wt% to about 3 wt%, about 0.05 wt% to about 1 wt%, about 0.05 wt% to about 0.7 wt%, about 0.05 wt% to about 0.5 wt%, about 0.1 wt% to about 10 wt%, about 0.1 wt% to about 7 wt%, about 0.1 wt% to about 5 wt%, about 0.1 wt% to about 3 wt%, about 0.1 wt% to about 1 wt%, about 0.1 wt% to about 0.7 wt%, about 0.1 wt% to about 0.5 wt%, about 0.3 wt% to about 10 wt%, about 0.3 wt% to about 7 wt%, about 0.3 wt% to about 5 wt%, about 0.3 wt% to about 3 wt%, about 0.3 wt% to about 1 wt%, about 0.3 wt% to about 0.7 wt%, about 0.5 wt% to about 0.7 wt%, about 0.3 wt% to about 0.5 wt%, or about 0.4 wt% to about 0.6 wt%.

[0084] acid

[0085] Acids, together with oxidants, can control the etching rate while etching at least a portion of the metal-containing film.

[0086] An acid can be a single type of acid or a mixture of two or more different acids.

[0087] Acids may include inorganic acids, organic acids, or any combination thereof.

[0088] In the implementation,

[0089] i) Acids can include inorganic acids,

[0090] ii) Acids may include organic acids, or

[0091] iii) Acids can include inorganic acids and organic acids.

[0092] For example, acids can include inorganic acids.

[0093] In one embodiment, the inorganic acid may include phosphoric acid, sulfuric acid, hydrochloric acid, or any combination thereof.

[0094] In another embodiment, the inorganic acid may include phosphoric acid.

[0095] In some implementations, the acid may include organic acids.

[0096] According to embodiments, the organic acid may include at least one of carboxylic acid, sulfonic acid, and phosphonic acid.

[0097] In some embodiments, the organic acid may include a carboxylic acid. For example, the carboxylic acid may include at least one of a non-amine-containing carboxylic acid and an amine-containing carboxylic acid. In some embodiments, the carboxylic acid contains... The number of -C(=O)OH can be selected from an integer from 1 to 10 or from 1 to 5.

[0098] In some embodiments, the organic acid may include an amine-free carboxylic acid. As used herein, the term "amine-free carboxylic acid" means that it does not contain amines. -N(R)- 'represents the part and by -N(R)(R') represents a partial carboxylic acid (where R and R' are each hydrogen or any substituent, and and Each of these is a binding site with an adjacent atom.

[0099] In some embodiments, the organic acid may not include amine-containing carboxylic acids. As used herein, the term "amine-containing carboxylic acid" refers to an organic acid containing amines. -N(R)- 'represents the part and / or the part by -N(R)(R') denotes a partial carboxylic acid, where R and R' are each hydrogen or any substituent, and and Each is a binding site with an adjacent atom.

[0100] In some embodiments, the organic acid may include monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, or any combination thereof. The number of carbon atoms contained in each monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid may be 1 to 31, 1 to 20, or 1 to 10.

[0101] In some embodiments, the organic acid may include amine-free monocarboxylic acids, amine-free dicarboxylic acids, amine-free tricarboxylic acids, or any combination thereof.

[0102] In some embodiments, the organic acid may be:

[0103] HCOOH;

[0104] Aliphatic compounds having 1 to 30 carbon atoms (e.g., 1 to 20 carbon atoms or 1 to 15 carbon atoms), or aromatic compounds having 6 to 30 carbon atoms (e.g., 6 to 15 carbon atoms or 6 to 10 carbon atoms), each being surrounded by at least one carboxylic acid group. -COOH) (e.g., 1, 2 or 3 carboxylic acid groups) substitution; or

[0105] Its combination.

[0106] In aliphatic and aromatic compounds, at least one hydrogen atom may optionally be replaced by a hydroxyl group, a thiol group, or a C1-C2 group. 10 Alkyl (e.g., C1-C5 alkyl), C1-C 10 Alkoxy groups (e.g., C1-C5 alkoxy groups), C1-C 10 Alkylthio (e.g., C1-C5 alkylthio), phenyl, or any combination thereof may be used instead.

[0107] In some embodiments, the aliphatic compound may be a saturated aliphatic compound (e.g., alkanes, cycloalkanes, etc.) or an unsaturated aliphatic compound (e.g., alkenes, alkynes, cycloalkenes, etc.).

[0108] In some embodiments, the aliphatic compound may be an acyclic aliphatic compound (e.g., alkanes, alkenes, alkynes, etc.) or a cyclic aliphatic compound (e.g., cycloalkanes, cycloolefins, adamantane, norbenzane, etc.).

[0109] In some embodiments, the aliphatic compound may be a straight-chain aliphatic compound (e.g., CH3-CH2-CH2-CH2-CH3, etc.) or a branched-chain aliphatic compound (e.g., CH3-CH(CH3)-CH2-CH3, CH3-C(CH3)2-CH3, etc.).

[0110] In some embodiments, the aromatic compound may be benzene.

[0111] In some embodiments, the organic acid may include formic acid, acetic acid (CH3COOH), propionic acid, butyric acid, valeric acid, lauric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, gallic acid, succinic acid, malic acid, maleic acid, crotonic acid, fumaric acid, ascorbic acid, glutamic acid, citric acid, tartaric acid, glycolic acid, lactic acid, benzoic acid, salicylic acid, or any combination thereof.

[0112] In one or more embodiments,

[0113] i) Acids may include phosphoric acid, or

[0114] ii) Acids may include phosphoric acid and non-amine-containing carboxylic acids (e.g., acetic acid, etc.).

[0115] In the implementation,

[0116] i) Acids can include inorganic acids.

[0117] ii) Acids may include organic acids, or

[0118] iii) Acids may include inorganic acids and organic acids, and among them

[0119] Inorganic acids may include phosphoric acid, and organic acids may include carboxylic acids (e.g., acetic acid).

[0120] Based on 100% by weight of the composition, the amount (by weight) of acid may be, for example, about 10% by weight to about 90% by weight, about 10% by weight to about 85% by weight, about 10% by weight to about 80% by weight, about 10% by weight to about 75% by weight, about 10% by weight to about 70% by weight, about 30% by weight to about 90% by weight, about 30% by weight to about 85% by weight, about 30% by weight to about 80% by weight, about 30% by weight to about 75% by weight, about 30% by weight to about 70% by weight, about 50% by weight to about 90% by weight, about 50% by weight to about 85% by weight, about 50% by weight to about 80% by weight, about 50% by weight to about 75% by weight, about 50% by weight to about 70% by weight, about 60% by weight to about 90% by weight, about 60% by weight to about 85% by weight, about 60% by weight to about 80% by weight, about 60% by weight to about 75% by weight, or about 60% by weight to about 70% by weight.

[0121] According to embodiments, the acid may include an inorganic acid, and based on 100% by weight of the composition, the amount (by weight) of the inorganic acid may be, for example, about 10% by weight to about 85% by weight, about 15% by weight to about 85% by weight, about 20% by weight to about 85% by weight, about 25% by weight to about 85% by weight, about 30% by weight to about 85% by weight, about 35% by weight to about 85% by weight, about 40% by weight to about 85% by weight, about 45% by weight to about 85% by weight, about 50% by weight to about 85% by weight, about 55% by weight to about 85% by weight. About 10 wt% to about 80 wt%, about 15 wt% to about 80 wt%, about 20 wt% to about 80 wt%, about 25 wt% to about 80 wt%, about 30 wt% to about 80 wt%, about 35 wt% to about 80 wt%, about 40 wt% to about 80 wt%, about 45 wt% to about 80 wt%, about 50 wt% to about 80 wt%, about 55 wt% to about 80 wt%, about 10 wt% to about 75 wt%, about 15 wt% to about 75 wt%, about 20 wt% to about 75 wt%, about 25 wt% % to about 75% by weight, about 30% by weight to about 75% by weight, about 35% by weight to about 75% by weight, about 40% by weight to about 75% by weight, about 45% by weight to about 75% by weight, about 50% by weight to about 75% by weight, about 55% by weight to about 75% by weight, about 10% by weight to about 70% by weight, about 15% by weight to about 70% by weight, about 20% by weight to about 70% by weight, about 25% by weight to about 70% by weight, about 30% by weight to about 70% by weight, about 35% by weight to about 70% by weight, about 40% by weight to about 70% by weight By weight%, about 45% to about 70% by weight, about 50% to about 70% by weight, about 55% to about 70% by weight, about 10% to about 65% by weight, about 15% to about 65% by weight, about 20% to about 65% by weight, about 25% to about 65% by weight, about 30% to about 65% by weight, about 35% to about 65% by weight, about 40% to about 65% by weight, about 45% to about 65% by weight, about 50% to about 65% by weight, or about 55% to about 65% by weight.

[0122] In some embodiments, the acid may include an organic acid, and based on 100% by weight of the composition, the amount of organic acid may be from about 0.1% by weight to about 15% by weight, from about 0.5% by weight to about 15% by weight, from about 1% by weight to about 15% by weight, from about 3% by weight to about 15% by weight, from about 5% by weight to about 15% by weight, from about 7% by weight to about 15% by weight, from about 0.1% by weight to about 13% by weight, from about 0.5% by weight to about 13% by weight, from about 1% by weight to about 13% by weight, from about 3% by weight to about 13% by weight, from about 5% by weight to about 13% by weight, or from about 7% by weight to about 13% by weight.

[0123] In some embodiments, the acid may include organic and inorganic acids, and the weight ratio of organic acid to inorganic acid may be in the range of 1:1 to 1:20, 1:3 to 1:10, or 1:5 to 1:7. For example, the acid may include organic and inorganic acids, and the weight ratio of organic acid to inorganic acid may be 1:6.

[0124] In some embodiments, the acid may include inorganic acid and organic acid, and the weight ratio of inorganic acid to organic acid may be in the range of 1:1 to 1:20, 1:3 to 1:10, or 1:5 to 1:7.

[0125] Etching control agent

[0126] Etching control agents, together with acids, can interact with individual metal atoms in a metal-containing film (which is the target film) to control the etching rate, etc.

[0127] The etching control agent may include at least one of the following: a compound represented by Formula 1 and a polymer comprising repeating units represented by Formula 2 (i.e., (i) a compound represented by Formula 1, (ii) a polymer comprising repeating units represented by Formula 2, or (iii) a compound represented by Formula 1 and a polymer comprising repeating units represented by Formula 2):

[0128] Formula 1

[0129]

[0130] Formula 2

[0131]

[0132] Among them, in equations 1 and 2,

[0133] R1 and R2 can be independently defined as follows:

[0134] Hydrogen, halogen atoms, -OH、 -SH or -C(=O)OH;

[0135] Each of the following C1-C that was not replaced or was replaced by: 30 Alkyl, C2-C 30 alkenyl, C1-C 30 Alkoxy, C1-C 30 Alkylthio, C3-C 30 Carbocyclic groups or C1-C 30 Heterocyclic groups: halogen atoms, -OH、 -SH、 -C(=O)OH, Cl-C 30Alkyl, C2-C 30 alkenyl, C1-C 30 Alkoxy, C1-C 30 alkylthio group or any combination thereof; or

[0136] -N(R 13 (R) 14 ),

[0137] R 11 To R 14 Each can be independently:

[0138] Hydrogen, halogen atoms, -OH、 -SH or -C(=O)OH; or

[0139] Each of the following C1-C that was not replaced or was replaced by: 30 Alkyl, C2-C 30 alkenyl, C1-C 30 Alkoxy, C1-C 30 Alkylthio, C3-C 30 Carbocyclic groups or C1-C 30 Heterocyclic groups: halogen atoms, -OH、 -SH、 -C(=O)OH, Cl-C 30 Alkyl, C2-C 30 alkenyl, C1-C 30 Alkoxy, C1-C 30 alkylthio groups or any combination thereof,

[0140] L1 to L3 can each be independently defined as follows:

[0141] Single key, O or S; or

[0142] Each of the following C1-C that was not replaced or was replaced by: 30 Alkylene, C2-C 30 alkenyl, C3-C 30 Carbocyclic groups or C1-C 30 Heterocyclic groups: halogen atoms, -OH、 -SH、 -C(=O)OH, Cl-C 30 Alkyl, C2-C 30 alkenyl, C1-C 30 Alkoxy, C1-C 30 alkylthio groups or any combination thereof,

[0143] a1 to a3 can each be an integer from 1 to 30 independently, and

[0144] and Each represents a binding site with an adjacent atom.

[0145] In the implementation,

[0146] i) The etching control agent may include a compound represented by Formula 1, or

[0147] ii) The etching control agent may include: a polymer comprising repeating units represented by Formula 2, or

[0148] iii) Etching control agents may include compounds represented by Formula 1 and polymers comprising repeating units represented by Formula 2.

[0149] According to the implementation method, R1 and R2 in Equations 1 and 2 can each be independently defined as follows:

[0150] -OH、 -SH or -C(=O)OH,

[0151] Each of the following C1-C that was not replaced or was replaced by: 10 Alkyl, C1-C 10 Alkoxy or C1-C 10 Alkyl thio: -OH、 -SH、 -C(=O)OH, Cl-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 alkylthio group or any combination thereof; or

[0152] -N(R 13 (R) 14 ).

[0153] In some implementations, R1 and R2 in Equations 1 and 2 can be independent of each other:

[0154] -OH;

[0155] Each of the following C1-C that was not replaced or was replaced by: 10 Alkyl (e.g., methyl, ethyl, etc.) or C1-C 10 Alkyl groups (e.g., methoxy, ethoxy, etc.): -OH, Cl-C 10 alkoxy or any combination thereof; or

[0156] -N(R 13 (R) 14 ).

[0157] In some implementations, R1 in Equation 2 may be... -N(R 13 (R) 14 ).

[0158] In some implementations, R in Equations 1 and 2 11 To R 14 Each can be independently:

[0159] hydrogen, -OH、 -SH or -C(=O)OH; or

[0160] Each of the following C1-C that was not replaced or was replaced by: 10 Alkyl, C1-C 10 Alkoxy or C1-C 10 Alkyl thio: -OH、 -SH、 -C(=O)OH, Cl-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Alkylthio group or any combination thereof.

[0161] In some implementations, R in Equation 1 11 To R 14 Each can be independently:

[0162] Hydrogen; or

[0163] C1-C that has not been replaced or has been replaced by the following: 10 Alkyl groups (e.g., methyl, ethyl, etc.): -OH, Cl-C 10 Alkoxy (e.g., methoxy, ethoxy, etc.) or any combination thereof.

[0164] In some implementations, R in Equation 2 11 To R 14 Each can be independently represented as either unsubstituted or substituted by the following C1-C 10 Alkyl groups (e.g., methyl, ethyl, etc.): -OH, Cl-C 10 Alkoxy (e.g., methoxy, ethoxy, etc.) or any combination thereof.

[0165] In some implementations, L1 to L3 in Equation 2 can each be independently...

[0166] Single key, O or S; or

[0167] C1-C that has not been replaced or has been replaced by the following: 10 Alkylenes (e.g., methylene, ethylene, etc.): -OH、 -SH、 -C(=O)OH, Cl-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Alkylthio group or any combination thereof.

[0168] In some implementations, L1 to L3 in Equation 2 can each be independently:

[0169] O or S; or

[0170] C1-C that has not been replaced or has been replaced by the following: 10 Alkylenes (e.g., methylene, ethylene, etc.): -OH、 -SH、 -C(=O)OH, Cl-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Alkylthio group or any combination thereof.

[0171] In some implementations, a1 to a3, which represent the number of L1 to L3 in Equation 2, can each be an integer from 1 to 5 (e.g., 1 or 2). When a1 is 2 or greater, two or more L1s can be the same or different from each other; when a2 is 2 or greater, two or more L2s can be the same or different from each other; and when a3 is 2 or greater, two or more L3s can be the same or different from each other.

[0172] In some implementations, in Equation 2,

[0173] L1 and L2 can each independently be C1-C that is not substituted or is substituted by the following: 10 Alkylenes (e.g., methylene, ethylene, etc.): -OH、 -SH、 -C(=O)OH, Cl-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 alkylthio groups or any combination thereof,

[0174] a1 and a2 can each be 1.

[0175] L3 can be O or S, and

[0176] a3 can be 1.

[0177] In some embodiments, the compound represented by Formula 1 may be a compound represented by Formula 1A.

[0178] In some implementations, the repeating unit represented by Equation 2 may be the repeating unit represented by Equation 2A:

[0179] Formula 1A Formula 2A

[0180]

[0181] Among them, in equations 1A and 2A,

[0182] R 11 To R 14 Each as described in this article,

[0183] R 15 and R 16 Each can be as follows regarding R 13 As described,

[0184] R 21 To R 24 Each can independently be a hydrogen atom, halogen atom, -OH、 -SH、 -C(=O)OH, Cl-C 30 Alkyl, C2-C 30 alkenyl, C1-C 30 Alkoxy or C1-C 30 Alkylthio group, and

[0185] and Each represents a binding site with an adjacent atom.

[0186] For example, R in Equation 1A 11 To R 16 Each can be independently:

[0187] Hydrogen; or

[0188] C1-C that has not been replaced or has been replaced by the following: 10 Alkyl groups (e.g., methyl, ethyl, etc.): -OH, Cl-C 10 Alkoxy (e.g., methoxy, ethoxy, etc.) or any combination thereof.

[0189] In some implementations, R in Formula 2A 11 To R 14 Each can be independently C1-C that has not been substituted or has been substituted by the following: 10Alkyl groups (e.g., methyl, ethyl, etc.): -OH, Cl-C 10 Alkoxy (e.g., methoxy, ethoxy, etc.) or any combination thereof, and R 21 To R 24 Each can be either hydrogen or methyl.

[0190] In some embodiments, the polymer comprising the repeating unit represented by Formula 2 may further comprise any repeating unit different from the repeating unit represented by Formula 2. For example, the polymer comprising the repeating unit represented by Formula 2 may further comprise repeating units derived from (obtained from) sulfur dioxide-containing compounds, repeating units derived from amide-containing compounds, repeating units derived from carboxylic acid-containing compounds, or any combination thereof. For example, amide-containing compounds may include acrylamide (CH2=CHC(O)NH2), methacrylamide (CH2=C(CH3)C(O)NH2), diacetone acrylamide, N,N-dimethylacrylamide, or any combination thereof, and carboxylic acid-containing compounds may include acrylic acid derived from alcohols having 1 to 30 carbon atoms (derived from alcohols having 1 to 30 carbon atoms), methacrylic acid derived from alcohols having 1 to 30 carbon atoms (derived from alcohols having 1 to 30 carbon atoms), unsaturated dicarboxylic acids having 1 to 30 carbon atoms (e.g., maleic acid), or any combination thereof.

[0191] In some embodiments, the weight-average molecular weight of the polymer comprising repeating units represented by Formula 2 may be, for example, about 200 g / mol to about 100,000 g / mol, about 200 g / mol to about 10,000 g / mol, about 200 g / mol to about 1,000 g / mol, or about 200 g / mol to about 500 g / mol. In some embodiments, the number-average molecular weight of the polymer comprising repeating units represented by Formula 2 may be, for example, about 200 to about 100,000, about 200 to about 10,000, about 200 to about 1,000, or about 200 to about 500. The weight-average molecular weight and number-average molecular weight may be measured, for example, using gel permeation chromatography (GPC), and may be calculated using polystyrene.

[0192] In some embodiments, the compound represented by Formula 1 may be one of compounds 1 to 19:

[0193]

[0194]

[0195]

[0196]

[0197] .

[0198] In some embodiments, the polymer comprising the repeating unit represented by Formula 2 may be one of polymers P1 to P4:

[0199]

[0200] .

[0201] The value of n in polymers P1 to P4 can be an integer greater than or equal to 2 (e.g., 2 to 100,000), and and Each represents a binding site with an adjacent atom.

[0202] Polymers P1 to P4 may each have a weight-average molecular weight or a number-average molecular weight within the range described herein.

[0203] C1-C in this instruction manual 30 Alkyl and C1-C 10 The alkyl group can be straight-chain or branched, and can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc.

[0204] C1-C in this instruction manual 30 Alkylene and C1-C 10 The alkylene group can be straight-chain or branched, and can be, for example, methylene, ethylene, etc.

[0205] C2-C in this instruction manual 30 alkenyl, C2-C 10 alkenyl and C2-C 30 Each of the sub-alkenyl groups has the same C2-C structure as described herein. 30 Alkyl, C2-C 10 Alkyl and C2-C 30 Alkylenes have the same structure and include at least one carbon-carbon double bond in the molecule.

[0206] C1-C 30 Alkoxy and C1-C 10 Alkyl groups are composed of -OR' represents a group (R' is C1-C as described in this article). 30 Alkyl or C1-C 10 Alkyl), and C1-C 30 Alkyl thiols and C1-C 10 Alkyl thio group is composed of -SR' represents a group (R' is C1-C as described in this document). 30 Alkyl or C1-C10 alkyl).

[0207] C3-C as used in this article 30 The carbocyclic group can be, for example, a cyclopentyl group, a cyclohexyl group, a phenyl group, a naphthyl group, etc.

[0208] C1-C in this instruction manual 30 Heterocyclic groups can be, for example, pyridine groups, pyrimidine groups, etc.

[0209] Based on 100% by weight of the composition, the amount (by weight) of the etching control agent may be from about 0.01% by weight to about 5% by weight, from about 0.01% by weight to about 4% by weight, from about 0.01% by weight to about 3% by weight, from about 0.01% by weight to about 2% by weight, from about 0.01% by weight to about 1.5% by weight, from about 0.01% by weight to about 1% by weight, from about 0.05% by weight to about 5% by weight, from about 0.05% by weight to about 4% by weight, from about 0.05% by weight to about 3% by weight, from about 0.05% by weight to about 2% by weight, from about 0.05% by weight... From approximately 0.5% to 1.5% by weight, from approximately 0.05% by weight to approximately 1% by weight, from approximately 0.1% by weight to approximately 5% by weight, from approximately 0.1% by weight to approximately 4% by weight, from approximately 0.1% by weight to approximately 3% by weight, from approximately 0.1% by weight to approximately 2% by weight, from approximately 0.1% by weight to approximately 1.5% by weight, from approximately 0.1% by weight to approximately 1% by weight, from approximately 0.5% by weight to approximately 5% by weight, from approximately 0.5% by weight to approximately 4% by weight, from approximately 0.5% by weight to approximately 3% by weight, from approximately 0.5% by weight to approximately 2% by weight, or from approximately 0.5% by weight to approximately 1.5% by weight. When the etching control agent comprises a polymer comprising repeating units represented by Formula 2, the amount of polymer refers to the amount of the polymer's solid content.

[0210] According to an embodiment, the etching control agent may include a compound represented by Formula 1 and a polymer comprising repeating units represented by Formula 2, and the weight ratio (based on polymer solid content) of the compound represented by Formula 1 and the polymer comprising repeating units represented by Formula 2 may be in the range of 1:1 to 1:100, 1:3 to 1:50, or 1:3 to 1:10. For example, the etching control agent may include a compound represented by Formula 1 and a polymer comprising repeating units represented by Formula 2, and the weight ratio (based on polymer solid content) of the compound represented by Formula 1 and the polymer comprising repeating units represented by Formula 2 may be 1:5.

[0211] pH

[0212] The compositions described above may have the following pH values: 5.0 or less, 4.0 or less, 3.0 or less, 2.2 or less, 2.0 or less, 1.0 or less, 0.5 or less, 0 or less, about -3.0 to about 5.0, about -3.0 to about 4.0, about -3.0 to about 3.0, about -3.0 to about 2.2, about -3.0 to about 2.0, about -3.0 to about 1.0, about -3.0 to about 0.5. Approximately -3.0 to approximately 0; approximately -2.5 to approximately 5.0; approximately -2.5 to approximately 4.0; approximately -2.5 to approximately 3.0; approximately -2.5 to approximately 2.2; approximately -2.5 to approximately 2.0; approximately -2.5 to approximately 1.0; approximately -2.5 to approximately 0.5; approximately -2.5 to approximately 0; approximately -2.0 to approximately 5.0; approximately -2.0 to approximately 4.0; approximately -2.0 to approximately 3.0; approximately -2.0 to approximately 2.2; approximately -2.0 to approximately... 2.0, about -2.0 to about 1.0, about -2.0 to about 0.5, about -2.0 to about 0, about -1.5 to about 5.0, about -1.5 to about 4.0, about -1.5 to about 3.0, about -1.5 to about 2.2, about -1.5 to about 2.0, about -1.5 to about 1.0, about -1.5 to about 0.5, about -1.5 to about 0, about -1.0 to about 5.0, about -1.0 to about 4.0, about -1. 0 to about 3.0, about -1.0 to about 2.2, about -1.0 to about 2.0, about -1.0 to about 1.0, about -1.0 to about 0.5, about -1.0 to about 0, about -0.6 to about 5.0, about -0.6 to about 4.0, about -0.6 to about 3.0, about -0.6 to about 2.2, about -0.6 to about 2.0, about -0.6 to about 1.0, about -0.6 to about 0.5, or about -0.6 to about 0. When the composition has such a pH range as described above, the interaction between the etching control agent and the metal atoms in the metal-containing film can occur more smoothly.

[0213] According to an embodiment, the composition may include about 0.001% to about 10% by weight of an oxidant, about 10% to about 85% by weight of an acid, and about 0.01% to about 3% by weight of an etch control agent.

[0214] According to an embodiment, the composition may include about 0.001 wt% to about 5 wt% of an oxidant, about 10 wt% to about 88 wt% of an acid, and about 0.01 wt% to about 5 wt% of an etch control agent.

[0215] According to an embodiment, the composition may include about 0.001% to about 5% by weight of an oxidant, about 10% to about 85% by weight of an acid, and about 0.01% to about 5% by weight of an etch control agent.

[0216] According to embodiments, the composition can be used in metal-containing film processing processes, such as etching processes and cleaning processes for metal-containing films. Metal-containing films are as described herein.

[0217] Alternatively, the composition may also be used as an etching byproduct remover, a post-etching process byproduct remover, an ashing process byproduct remover, a cleaning composition, a photoresist (PR) remover, an etching composition for packaging processes, a cleaning agent for packaging processes, a wafer adhesive material remover, an etchant, a post-etching residue stripper, an ashing residue cleaner, a photoresist residue stripper, a chemical mechanical polishing (CMP) cleaner, or a post-CMP cleaner.

[0218] Methods for treating metal-containing films

[0219] Using the composition described above, metal-containing films comprising a first region and a second region can be processed more effectively, wherein the material in the first region differs from the material included in the second region. For a description of the metal-containing film, the first region, and the second region, refer to the description herein.

[0220] According to the embodiments, the first region and the second region may independently include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), cobalt (Co), copper (Cu), or any combination thereof.

[0221] According to another embodiment, the first region may include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), or any combination thereof, and the second region may include tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

[0222] According to another embodiment, the first region may include a metal nitride, a metal oxynitride, or any combination thereof, and the second region may include a conductive metal.

[0223] According to another embodiment, the first region may include titanium nitride, titanium oxynitride, or any combination thereof, and each of the titanium nitride and titanium oxynitride may optionally further include indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

[0224] Figure 1A and 2 This is a diagram illustrating an embodiment of a metal-containing membrane treatment method.

[0225] Reference Figure 1A A substrate 10 is provided having a metal-containing film 20A. Although in Figure 1AAlthough not shown, various circuit elements may optionally be additionally disposed between the substrate 10 and the metal-containing film 20A.

[0226] The metal-containing film 20A may include a first region 21 and a second region 22. The first region 21 and the second region 22 may be disposed separately from each other or may be disposed at least partially in contact with each other, and the metal-containing film 20A may have various patterns. The metal-containing film 20A including the first region 21 and the second region 22 may contact the composition 30, thereby removing a portion of the metal-containing film 20A. For example, the metal-containing film 20A may contact the composition 30 during etching, cleaning, and / or polishing processes. The composition 30 may include oxidants, acids, and etching control agents as described herein, and for a detailed description thereof, refer to the description herein.

[0227] The etching rate ratio obtained by dividing the first etching rate of the composition 30 etching the first region 21 by the second etching rate of the composition 30 etching the second region 22 can be 0.04 or greater. For example, the etching rate ratio obtained by dividing the first etching rate of the composition 30 etching the first region 21 by the second etching rate of the composition 30 etching the second region 22 may be about 0.05 or greater, about 0.06 or greater, about 0.04 to about 1.0, about 0.05 to about 1.0, about 0.06 to about 1.0, about 0.04 to about 0.5, about 0.05 to about 0.5, about 0.06 to about 0.5, about 0.04 to about 0.3, about 0.05 to about 0.3, about 0.06 to about 0.3, about 0.04 to about 0.2, about 0.05 to about 0.2, about 0.06 to about 0.2, about 0.04 to about 0.15, about 0.05 to about 0.15, about 0.06 to about 0.15, or about 0.06 to about 0.13.

[0228] Figure 1B This is a schematic diagram illustrating the surface of the metal-containing film 20A that can contact the composition 30. The etched area ratio, obtained by dividing the first area of ​​the first region 21 exposed to contact the composition 30 by the second area of ​​the second region 22 exposed to contact the composition 30, can be about 0.05 to about 1.0, about 0.05 to about 0.9, about 0.05 to about 0.7, about 0.05 to about 0.5, about 0.05 to about 0.4, about 0.05 to about 0.3, or about 0.05 to about 0.2.

[0229] When the metal-containing film 20A comes into contact with the composition 30, the high reactivity of the metal included in the metal-containing film 20A (e.g., the metal such as molybdenum contained in the second region 22) can be controlled through the interaction of the oxidant, acid, and etching control agent included in the composition 30. As a result, the etching rate (e.g., the etching rate of the second region 22) in the regions containing relatively highly reactive metals in the first region 21 and the second region 22 can be appropriately controlled. Therefore, portions of both the first region 21 and the second region 22 can be etched, allowing the formation of... Figure 2 The metal-containing film pattern 20 shown has a substantially flat surface (e.g., a small step height difference or no step height difference between the first region 21 and the second region 22).

[0230] Figure 3 and 4 This is a diagram illustrating another embodiment of a metal-containing membrane treatment method.

[0231] refer to Figure 3 A substrate 10 is provided, wherein, in addition to the metal-containing film 20A, an additional material 40 is provided adjacent to the metal-containing film 20A. For Figure 3 For a description of the metal-containing film 20A and the substrate 10, please refer to [reference needed]. Figure 1A .

[0232] Figure 3 The additional material 40 may be disposed spaced apart from the metal-containing membrane 20A or may be at least partially in contact with it. As used herein, the term "additional material 40" refers to a material different from the metal-containing membrane 20A that is disposed adjacent to the metal-containing membrane 20A and located in an area that may be affected by the composition 30 during the treatment of the metal-containing membrane 20A using the composition 30.

[0233] The additional material 40 may include at least one of an insulating material and a semiconductor material. The insulating material and the semiconductor material may include a variety of known materials.

[0234] Insulating materials may include various oxides, nitrides, oxynitrides, high-dielectric materials, or combinations thereof. For example, insulating materials may include silicon oxides, silicon nitrides, silicon oxynitrides, aluminum oxides, hafnium oxides, hafnium oxynitrides, zirconium oxides, or combinations thereof. Hafnium oxides and hafnium oxynitrides may optionally further include Si, Ta, Ti, Zr, or any combination thereof. As another example, insulating materials may include tetraethyl orthosilicate (TEOS), hydrogen silsesquioxane (HSQ), methyl silsesquioxane (MSQ), etc.

[0235] Semiconductor materials may be, for example, materials included in channels, and may include: group IV semiconductor materials such as silicon, germanium (Ge), silicon-germanium (SiGe), and silicon carbide (SiC); group III-V semiconductor materials such as gallium arsenide (GaAs), indium arsenide (InAs), and indium phosphide (InP); and oxide semiconductors, nitride semiconductors, and oxynitride semiconductors. Oxide semiconductors may include, for example, indium gallium zinc oxide (IGZO), indium tin zinc oxide (ITZO), indium tin gallium oxide (ITGO), indium tungsten oxide (IWO), indium tin oxide (ITO), ZnO, Cu2O, or any combination thereof.

[0236] like Figure 3 As shown, a metal-containing film 20A, including a first region 21 and a second region 22, and additional material 40 can be contacted with the composition 30, and a portion of the metal-containing film 20A can be removed. For example, the metal-containing film 20A can be contacted with the composition 30 during etching, cleaning, and / or polishing processes of the metal-containing film 20A, including the first region 21 and the second region 22. The composition 30 includes an oxidant, an acid, and an etching control agent as described in this specification, and for a detailed description thereof, refer to the description herein.

[0237] When the metal-containing film 20A comes into contact with the composition 30, a portion of the metal-containing film 20A can be removed. Specifically, during contact between the metal-containing film 20A and the composition 30, the high reactivity of the metal included in the metal-containing film 20A (e.g., the metal such as molybdenum included in the second region 22) can be controlled due to the interaction between the oxidant, acid, and etching control agent included in the composition 30. As a result, the etching rate (e.g., the etching rate of the second region 22) of the regions in the first region 21 and the second region 22 containing the relatively highly reactive metal can be appropriately controlled, such that portions of both the first region 21 and the second region 22 are etched. Therefore, as Figure 4 As shown, a metallic film pattern 20 with a substantially flat surface (e.g., a small step height difference or no step height difference between the first region 21 and the second region 22) can be formed. Additionally, an additional material 40, for example comprising at least one insulating material and a semiconductor material, can remain substantially undamaged by the composition 30.

[0238] Methods for manufacturing electronic devices

[0239] Using the above-described composition, high-quality electronic devices can be manufactured. Therefore, a method for manufacturing electronic devices using the described composition can be provided.

[0240] According to one aspect of this disclosure,

[0241] Provides a method for manufacturing electronic devices including transistors.

[0242] The transistor includes,

[0243] Ditch;

[0244] The source and drain electrodes are spaced apart from each other and electrically connected to the channel;

[0245] Gate electrode; and

[0246] A gate insulating film disposed between the gate electrode and the channel.

[0247] The method includes:

[0248] Provides a barrier layer comprising metal nitrides, metal oxynitrides, or combinations thereof;

[0249] Provides a conductive layer comprising a conductive metal; and

[0250] A gate electrode is formed by contacting the barrier layer and the conductive layer with the composition to etch a portion of the barrier layer and a portion of the conductive layer.

[0251] According to one aspect of this disclosure, a method of manufacturing an electronic device may include: forming a structure comprising source and drain electrodes spaced apart from each other and electrically connected to a channel; and providing a gate electrode and a gate insulating film on the structure, wherein the gate insulating film is located between the gate electrode and the channel. The gate electrode may be provided by: providing a barrier layer comprising a metal nitride, a metal oxynitride, or any combination thereof; providing a conductive layer comprising a conductive metal; and forming the gate electrode by contacting the barrier layer and the conductive layer with the composition to etch a portion of the barrier layer and a portion of the conductive layer.

[0252] The channel may include, for example, semiconductor materials as described herein. For example, the channel may include: group IV semiconductor materials such as silicon, germanium (Ge), silicon-germanium (SiGe), and silicon carbide (SiC); group III-V semiconductor materials such as gallium arsenide (GaAs), indium arsenide (InAs), and indium phosphide (InP); oxide semiconductors, nitride semiconductors, and oxynitride semiconductors. Oxide semiconductors may include, for example, indium gallium zinc oxide (IGZO), indium tin zinc oxide (ITZO), indium tin gallium oxide (ITGO), indium tungsten oxide (IWO), indium tin oxide (ITO), ZnO, Cu2O, or any combination thereof.

[0253] The gate insulating film may include an insulating material capable of electrically insulating the gate electrode from the channel. For example, the gate insulating film may include various oxides, nitrides, oxynitrides, high-k materials, or combinations thereof. For example, the gate insulating film may include silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, hafnium oxide, hafnium oxynitride, zirconium oxide, or combinations thereof. Hafnium oxide and hafnium oxynitride may optionally further include Si, Ta, Ti, Zr, or any combination thereof.

[0254] The gate electrode may include a barrier layer and a conductive layer. The barrier layer may be disposed, for example, between a gate insulating film and a conductive layer.

[0255] To provide a gate electrode, a barrier layer and a conductive layer may be provided. For example, after forming the barrier layer, a conductive layer may be formed on the surface of the barrier layer. However, depending on the structure of the channel and / or the gate electrode, various modifications are possible, such as forming a barrier layer on the surface of the conductive layer after forming the conductive layer.

[0256] A barrier layer may be provided to limit and / or prevent the peripheral (peripheral) diffusion of conductive metals (e.g., metal ions) included in the conductive layer and / or promote the smooth deposition of the conductive layer.

[0257] For a detailed description of each of the metal nitrides and / or metal oxynitrides that may be included in the barrier layer, please refer to the description of each of the metal nitrides and / or metal oxynitrides that may be included in the first region of the metal-containing film herein.

[0258] According to an embodiment, the barrier layer may include titanium nitride, titanium oxynitride, or a combination thereof, and each of the titanium nitride and titanium oxynitride may optionally further include indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

[0259] For a detailed description of the conductive metal that may be included in the conductive layer, please refer to the description of the conductive metal that may be included in the second region of the metal-containing film herein.

[0260] According to embodiments, the conductive layer may include tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

[0261] Subsequently, the barrier layer and the conductive layer can be contacted with the composition described herein to etch a portion of the barrier layer and a portion of the conductive layer, thereby forming a gate electrode.

[0262] When the barrier layer and conductive layer are brought into contact with the composition as described herein, the high reactivity of the conductive metal included in the conductive layer can be controlled by the interaction between the oxidant, acid, and etch control agent in the composition. As a result, the etch rate of the conductive layer can be appropriately controlled, allowing portions of both the barrier layer and the conductive layer to be etched. Therefore, a gate electrode with a substantially flat surface (e.g., a small step height difference or no step height difference between the barrier layer and the conductive layer) can be formed. Furthermore, since at least one of the channels and gate insulating film disposed adjacent to the gate electrode can be substantially undamaged by the composition, high-quality electronic devices including gate electrodes with precise patterns can be manufactured without damaging the areas adjacent to the gate electrode.

[0263] Electronic devices can be semiconductor devices.

[0264] For example, electronic devices may include volatile memory devices such as dynamic random access memory (“DRAM”) devices or static random access memory (“SRAM”) devices, resistive random access memory (“ReRAM”) devices, electrically erasable programmable read-only memory (“EEPROM”) devices, flash memory (which may also be considered a subset of EEPROM) devices, ferroelectric random access memory (“FRAM”) devices, magnetoresistive random access memory (“MRAM”) devices, and non-volatile memory devices such as other semiconductor devices capable of storing information.

[0265] According to the implementation method, the electronic device may be a DRAM device.

[0266] In the following text, reference will be made to Figure 5 , 6A Sections 6B, 7, 8, and 9 describe the manufacturing methods of electronic devices in more detail.

[0267] Figure 5 Figure 6 is a schematic plan view of the electronic device 3000 according to the embodiment, and Figure 6 is... Figure 5 A perspective view of the electronic device 3000 shown. Figure 5 The electronic device 3000 can be a DRAM device.

[0268] Reference Figure 5 , 6A And 6B, the electronic device 3000 includes a plurality of unit elements 3100 arranged in an array. Each unit element 3100 has a 1T1C structure including a transistor and a capacitor (or consisting of a transistor and a capacitor).

[0269] Electronic device 3000 includes a transistor structure 100 and a plurality of capacitors 3500 provided to the transistor structure 100. The transistor structure 100 may be, for example, a vertical channel array transistor structure including channels arranged perpendicularly to a substrate (see [link to documentation]). Figure 6A ), or a channel array transistor structure comprising channels arranged and stacked horizontally relative to the substrate (see Figure 6B ).

[0270] In the transistor structure 100, a plurality of gate electrodes (or word lines) 150 and a plurality of bit lines 160 are provided to intersect each other. Each gate electrode 150 is provided to extend in a first direction (e.g., the x-axis direction), and each bit line 160 is provided to extend in a second direction (e.g., the y-axis direction) intersecting the first direction. The transistor is arranged at the points where the plurality of gate electrodes 150 and the plurality of bit lines 160 intersect.

[0271] Figures 7 to 9 It is an illustrative explanation Figure 6A A partial diagram of the manufacturing process of the transistor structure 100 shown.

[0272] exist Figure 7 In the transistor structure 100, there are a substrate 110 and a plurality of channels 140 arranged in an array on the substrate 110. The plurality of channels 140 may be arranged in a two-dimensional array on a plane (e.g., the xy plane) of the substrate 110.

[0273] Substrate 110 may include a semiconductor, such as silicon (Si). As a specific example, substrate 110 may be a silicon substrate doped with n-type impurities. However, this is merely illustrative. Alternatively, substrate 110 may include, for example, group IV semiconductor materials such as germanium (Ge), silicon germanium (SiGe), or silicon carbide (SiC); group III-V semiconductor materials such as gallium arsenide (GaAs), indium arsenide (InAs), or indium phosphide (InP); or oxide semiconductors, nitride semiconductors, oxynitride semiconductors, etc.

[0274] Multiple channels 140 may each be provided to extend vertically from the substrate 110. Each channel 140 may be provided to project vertically from the upper surface of the substrate 110. Each channel 140 may be integrally formed with the substrate 110 and may therefore include the same semiconductor material as the semiconductor substrate 110. Figure 7 In this diagram, the channel 140 is shown to be integrally formed with the substrate 110, but various modifications are possible, such as the channel 140 being formed separately from the substrate 110.

[0275] A source S and a drain D are provided at the bottom and top of each channel 140, respectively. The source S is provided to be electrically connected to the bottom of the channel 140, and the drain D is provided to be connected to the top of the channel 140. For example, the source S and drain D can be formed by forming doped regions. Figure 5 The capacitor 3500 shown can be connected to the drain D provided at the upper portion of the channel 140.

[0276] On the top surface of substrate 110, sources S are provided in an array corresponding to channels 140. Below the sources S, a plurality of bit lines 160 are provided extending along a second direction (e.g., the y-axis direction). Each bit line 160 is electrically connected to the sources S arranged along the second direction. The plurality of bit lines 160 may be formed in substrate 110 and therefore may comprise the same semiconductor material as substrate 110. Figure 7 In the middle, bit line 160 is formed using a material separate from substrate 110; however, various modifications are possible.

[0277] Multiple insulating materials 170 may be provided in the semiconductor substrate 110 between multiple bit lines 160. The multiple insulating materials 170 may be provided to extend in a second direction parallel to the multiple bit lines 160, thereby separating the multiple bit lines 160 within the semiconductor substrate 110. The insulating materials 170 may include, for example, silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, hafnium oxide, hafnium oxynitride, zirconium oxide, or combinations thereof.

[0278] A gate insulating film 130 is provided on the surface of the channel 140. The gate insulating film 130 may include an insulating material as described herein, such as silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, hafnium oxide, hafnium oxynitride, zirconium oxide, or combinations thereof.

[0279] In the substrate 110 provided with a channel 140 and a gate insulating film 130 as described above, a barrier layer 151 comprising a metal nitride, a metal oxynitride, or a combination thereof, and a conductive layer 152 comprising a conductive metal are provided in the trench at least partially defined by the gate insulating film 130, such as Figure 7 As shown in the diagram. For example, after forming the barrier layer 151, a conductive layer 152 may be formed on the surface of the barrier layer 151. However, depending on the structure of the channel 140 and / or the gate electrode 150, various modifications are possible, such as forming the barrier layer 151 on the surface of the conductive layer 152 after forming the conductive layer 152. For a description of the metal nitrides and / or metal oxynitrides included in the barrier layer 151 and the conductive metals included in the conductive layer 152, refer to the description herein.

[0280] Subsequently, as Figure 7 As shown, an embedded insulating layer 180 is provided in a trench at least partially defined by a conductive layer 152. The embedded insulating layer 180 can be used for protection. Figure 8 The gate electrode 150 is protected from the penetration of oxygen and other substances. After the embedded insulating layer 180 is formed, a planarization process can be performed to expose the top surfaces of the barrier layer 151 and the conductive layer 152.

[0281] Then, the exposed top surfaces of the barrier layer 151 and the conductive layer 152 are brought into contact with the composition 30 to etch a portion of the barrier layer 151 and a portion of the conductive layer 152, thereby forming a composition having Figure 8 The gate electrode 150 of the pattern shown. Figure 7 The composition 30 includes an oxidant, an acid, and an etching control agent as described in this specification, and for a detailed description thereof, refer to the description herein.

[0282] The etching rate ratio obtained by dividing the first etching rate of the composition 30 etching the barrier layer 151 by the second etching rate of the composition 30 etching the conductive layer 152 can be 0.04 or greater. For example, the etching rate ratio obtained by dividing the first etching rate of the composition 30 etching the barrier layer 151 by the second etching rate of the composition 30 etching the conductive layer 152 may be 0.05 or greater, about 0.06 or greater, about 0.04 to about 1.0, about 0.05 to about 1.0, about 0.06 to about 1.0, about 0.04 to about 0.5, about 0.05 to about 0.5, about 0.06 to about 0.5, about 0.04 to about 0.3, about 0.05 to about 0.3, about 0.06 to about 0.3, about 0.04 to about 0.2, about 0.05 to about 0.2, about 0.06 to about 0.2, about 0.04 to about 0.15, about 0.05 to about 0.15, about 0.06 to about 0.15, or about 0.06 to about 0.13.

[0283] Meanwhile, the etch area ratio obtained by dividing the first area of ​​the barrier layer 151 exposed to contact with the composition 30 by the second area of ​​the conductive layer 152 exposed to contact with the composition 30 can be about 0.05 to about 1.0, about 0.05 to about 0.9, about 0.05 to about 0.7, about 0.05 to about 0.5, about 0.05 to about 0.4, about 0.05 to about 0.3, or about 0.05 to about 0.2.

[0284] When the barrier layer 151 and the conductive layer 152 come into contact with the composition 30, the high reactivity of the conductive metal included in the conductive layer 152 can be controlled through the interaction between the oxidant, acid, and etching control agent contained in the composition 30. As a result, the etching rate of the conductive layer 152 can be appropriately controlled, and portions of both the barrier layer 151 and the conductive layer 152 can be etched. Therefore, as... Figure 8 As shown, a gate electrode 150 with a substantially flat top surface (e.g., a small step height difference or no step height difference between the barrier layer 151 and the conductive layer 152) can be formed. Furthermore, the channel 140, gate insulating film 130, and embedded insulating layer 180 arranged adjacent to the gate electrode 150 are substantially undamaged by the composition 30, enabling the manufacture of a high-quality electronic device 3000 with a precisely patterned gate electrode 150 without damaging the regions adjacent to the gate electrode 150, such as the channel 140, gate insulating film 130, and embedded insulating layer 180.

[0285] exist Figure 8 In this configuration, a plurality of gate electrodes 150 on the substrate 110 may be arranged to extend along a first direction (e.g., the x-axis direction). The first direction may be a direction intersecting the second direction described above. For example, the first direction may be a direction perpendicular to the second direction. However, it is not necessarily limited to this.

[0286] Each gate electrode 150 is provided to correspond to a channel 140 arranged along a first direction. Specifically, each gate electrode 150 is provided to surround a channel 140 arranged along the first direction. These gate electrodes 150 can function as word lines.

[0287] Multiple gate electrodes 150 may be provided to intersect with multiple insulating materials 170 provided below them. The top surface of the insulating material 170 may be provided to be adjacent to the bottom surface of the gate electrode 150. The top of the insulating material 170 may be provided to protrude from the bottom of the gate electrode 150, but is not limited thereto.

[0288] Subsequently, as Figure 9 As shown, an insulating layer 190 may be additionally provided on the surface of the etched barrier layer 151 and the surface of the etched conductive layer 152. The insulating layer 190 may be used to further insulate the gate electrode 150 from the channel 140 and may include, for example, an insulating material as described herein.

[0289] Methods of manufacturing electronic devices

[0290] Reference Figure 10 An embodiment of a method for manufacturing an electronic device may include: preparing a substrate S100 on which a metal-containing film is provided; contacting the metal-containing film with a composition as described herein S110; and manufacturing electronic components S120 using one or more subsequent processes. The subsequent processes may include various known processes for manufacturing electronic components, such as capacitor forming processes.

[0291] Examples 1 to 4, Comparative Examples C1 and C2

[0292] The compositions of Examples 1 to 4, Comparative Examples C1 and C2 were prepared by mixing an oxidant, an acid, and an etching control agent, the materials of which were weighed according to the amounts described in Table 1. The remainder of each composition corresponds to water (deionized water). The number-average molecular weight (Mn) of polymer P1 (Merck, methylated poly(melamine-co-formaldehyde)) is... n The value is 432, and the amount of polymer P1 described in Table 1 refers to the amount of solid content of polymer P1. The compositions of Examples 1 to 3 and Comparative Example C2 include one compound as an etching control agent, the composition of Example 4 includes two compounds as etching control agents, the composition of Comparative Example C1 does not include an etching control agent, and the composition of Comparative Example C2 does not include an oxidant.

[0293] Evaluation Example 1

[0294] The composition of Example 1 was placed in three separate beakers and heated to 60°C. Then, a titanium nitride film sample, a molybdenum film sample, and a silicon oxide film sample, each with a size of 1 cm × 1 cm, were immersed in the beakers for 1 minute. The thicknesses of the titanium nitride film, molybdenum film, and silicon oxide film were measured using an ellipsometer (M-2000, JAWoolam), a four-point resistance meter, and X-ray fluorescence spectroscopy (XRF) to obtain the etching rates of the titanium nitride film (also known as the "titanium nitride film etching rate"), the molybdenum film (also known as the "molybdenum film etching rate"), and the silicon oxide film (also known as the "silicon oxide film etching rate"). The etching rates of each film are expressed in Å / min. The molybdenum film etching rate "A" was then divided by the titanium nitride film etching rate "B" to evaluate the ratio "A / B" of the molybdenum film etching rate to the titanium nitride film etching rate.

[0295] The compositions of Examples 2 to 4, Comparative Examples C1 and C2 were repeatedly tested, and the molybdenum film etching rates of the compositions of Examples 1 to 4 and Comparative Example C2 were summarized in Table 1 as relative values ​​(%) to the molybdenum film etching rate of the composition of Comparative Example C1. The A / B ratios of the compositions of Examples 1 to 4 and Comparative Example C2 were also summarized in Table 1 as relative values ​​(%) to the A / B ratio of the composition of Comparative Example C1. The pH values ​​of the compositions of Examples 1 to 4, Comparative Examples C1 and C2, as evaluated by a pH meter, are also summarized in Table 1.

[0296] Table 1

[0297]

[0298]

[0299] From Table 1, if the molybdenum film and the titanium nitride-containing film are etched simultaneously, it can be confirmed that i) compared with the compositions of Examples 1 to 4, the composition of Comparative Example C1, which does not include the etching control agent, excessively etches the molybdenum film, and ii) the composition of Comparative Example C2, which does not include the oxidant, does not etch the molybdenum film. On the other hand, it can be confirmed that the compositions of Examples 1 to 4 can simultaneously etch both the titanium nitride-containing film and the molybdenum film at a more appropriate etching ratio, without substantially (basically) damaging the silicon oxide film and without excessively etching the molybdenum film, and therefore can be usefully used for more uniform etching of metal-containing films with multiple compositions.

[0300] Example 5 and Comparative Example C3

[0301] The compositions of Example 5 and Comparative Example C3 were prepared by mixing an oxidant, an acid, and an etching control agent, the materials of which were weighed according to the amounts described in Table 2. The compositions of Example 5 and Comparative Example C3 comprised two compounds as acids.

[0302] Evaluation Example 2

[0303] For the compositions of Example 5 and Comparative Example C3, pH and molybdenum film etching rate were evaluated according to the method described in Evaluation Example 1. The results are summarized in Table 2. In Table 2, the molybdenum film etching rate of the composition of Example 5 is expressed as a relative value (%) relative to the molybdenum film etching rate of the composition of Comparative Example C3.

[0304] Table 2

[0305]

[0306] As can be seen from Table 2, the composition of Comparative Example C3, which does not include an etching control agent, excessively etches the molybdenum film, while the composition of Example 5 can etch both the titanium nitride film and the molybdenum film at a more appropriate etching ratio, without substantially (basically) damaging the silicon oxide film and without excessively etching the molybdenum film, and is therefore useful for more uniform etching of metal-containing films with multiple compositions.

[0307] The compositions according to the embodiments facilitate control over the etching rate of various metal-containing films and are therefore effectively used in various processing techniques for metal-containing films, such as etching, cleaning, and polishing processes. By using the compositions to treat metal-containing films, higher quality electronic and / or semiconductor devices can be manufactured.

[0308] It should be understood that the embodiments described herein are to be considered in a descriptive sense only and are not intended for limiting purposes. The descriptions of features or aspects within each embodiment should typically be considered applicable to other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the accompanying drawings, those skilled in the art will understand that various changes in form and detail may be made therein without departing from the spirit and scope defined by the appended claims.

Claims

1. A composition comprising: Oxidizing agent; acid; and Etching control agent, in which The etching control agent comprises at least one of the following: a compound represented by Formula 1 and a polymer comprising repeating units represented by Formula 2. Formula 1 Formula 2 Among them, in equations 1 and 2, R1 and R2 are independent of each other: Hydrogen, halogen atoms, -OH、 -SH or -C(=O)OH; Each of the following C1-C that was not replaced or was replaced by: 30 Alkyl, C2-C 30 alkenyl, C1-C 30 Alkoxy, C1-C 30 Alkylthio, C3-C 30 Carbocyclic groups or C1-C 30 Heterocyclic groups: halogen atoms, -OH、 -SH、 -C(=O)OH, Cl-C 30 Alkyl, C2-C 30 alkenyl, C1-C 30 Alkoxy, C1-C 30 alkylthio group or any combination thereof; or -N(R 13 )(R 14 ), R 11 To R 14 Each independently is: Hydrogen, halogen atoms, -OH、 -SH or -C(=O)OH; or Each of the following C1-C that was not replaced or was replaced by: 30 Alkyl, C2-C 30 alkenyl, C1-C 30 Alkoxy, C1-C 30 Alkylthio, C3-C 30 Carbocyclic groups or C1-C 30 Heterocyclic groups: halogen atoms, -OH、 -SH、 -C(=O)OH, Cl-C 30 Alkyl, C2-C 30 alkenyl, C1-C 30 Alkoxy, C1-C 30 alkylthio groups or any combination thereof, L1 to L3 are each independent of: Single key, O or S; or Each of the following C1-C that was not replaced or was replaced by: 30 Alkylene, C2-C 30 alkenyl, C3-C 30 Carbocyclic groups or C1-C 30 Heterocyclic groups: halogen atoms, -OH、 -SH、 -C(=O)OH, Cl-C 30 Alkyl, C2-C 30 alkenyl, C1-C 30 Alkoxy, C1-C 30 alkylthio groups or any combination thereof, a1 to a3 are each independent integers from 1 to 30, and and Each represents a binding site with an adjacent atom.

2. The composition according to claim 1, wherein... The oxidant includes hydrogen peroxide.

3. The composition according to claim 1, wherein... Based on 100% by weight of the composition, the amount of the oxidant is from about 0.001% by weight to about 10% by weight.

4. The composition according to claim 1, wherein... The acid includes inorganic acids, or The acid includes organic acids, or The acid includes the inorganic acid and the organic acid.

5. The composition according to claim 1, wherein... The acid includes phosphoric acid.

6. The composition according to claim 1, wherein... The acid includes carboxylic acids.

7. The composition according to claim 1, wherein Based on 100% by weight of the composition, the amount of acid is from about 10% by weight to about 90% by weight.

8. The composition according to claim 1, wherein The acids include organic acids and inorganic acids, and The weight ratio of the organic acid to the inorganic acid is in the range of 1:1 to 1:

20.

9. The composition according to claim 1, wherein In equations 1 and 2, R1 and R2 are independently defined as follows: -OH、 -SH or -C(=O)OH; Each of the following C1-C that was not replaced or was replaced by: 10 Alkyl, C1-C 10 Alkoxy or C1-C 10 Alkyl thio: -OH、 -SH、 -C(=O)OH, Cl-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 alkylthio group or any combination thereof; or -N(R 13 )(R 14 ), R in Equations 1 and 2 11 To R 14 Each independently is: hydrogen, -OH、 -SH or -C(=O)OH; or Each of the following C1-C that was not replaced or was replaced by: 10 Alkyl, C1-C 10 Alkoxy or C1-C 10 Alkyl thio: -OH、 -SH、 -C(=O)OH, Cl-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Alkylthio group or any combination thereof.

10. The composition according to claim 1, wherein In Equation 2, L1 to L3 are each independently: O or S; or C1-C that has not been replaced or has been replaced by the following: 10 Alkylene: -OH、 -SH、 -C(=O)OH, Cl-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 alkylthio or any combination thereof, and a1 to a3 are each an independent integer from 1 to 5.

11. The composition according to claim 1, wherein The compound represented by Formula 1 is a compound represented by Formula 1A, and The repeating unit represented by Equation 2 is the repeating unit represented by Equation 2A: Formula 1A Formula 2A in, In equations 1A and 2A, R 11 To R 14 Each is the same as described in Equations 1 and 2. R 15 and R 16 Each as shown with respect to R in Equations 1 and 2 13 Described, R 21 To R 24 Each independently consists of hydrogen and halogen atoms. -OH、 -SH、 -C(=O)OH, Cl-C 30 Alkyl, C2-C 30 alkenyl, C1-C 30 Alkoxy or C1-C 30 Alkylthio group, and and Each represents a binding site with an adjacent atom.

12. The composition according to claim 1, wherein Based on 100% by weight of the composition, the amount of the etching control agent is from about 0.01% by weight to about 5% by weight.

13. A method for processing a metal-containing film, the method comprising: Prepare a substrate comprising the metal-containing film, the metal-containing film comprising a first region and a second region; as well as The metal-containing film is brought into contact with the composition according to any one of claims 1 to 12; The first region and the second region independently include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), cobalt (Co), copper (Cu), or any combination thereof. This includes materials in the first region that are different from materials included in the second region.

14. The method according to claim 13, The first region comprises titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), or any combination thereof, and The second region includes tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

15. The method according to claim 13, The first region includes metal nitrides, metal oxynitrides, or any combination thereof, and The second region includes conductive metal.

16. The method according to claim 13, The first region includes titanium nitride, titanium oxynitride, or any combination thereof, and each of the titanium nitride and the titanium oxynitride optionally further includes indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

17. The method according to claim 13, The etch area ratio is in the range of about 0.05 to about 1.0, and the etch area ratio is a ratio obtained by dividing the first area of ​​the first region exposed to contact with the composition by the second area of ​​the second region exposed to contact with the composition.

18. A method for manufacturing an electronic device including transistors, The transistor includes Ditch, The source and drain electrodes are spaced apart from each other and electrically connected to the channel. Gate electrode, and The gate insulating film between the gate electrode and the channel, and The method includes: Provides a barrier layer including metal nitrides, metal oxynitrides, or any combination thereof; Provides a conductive layer including a conductive metal; as well as The gate electrode is formed by contacting the barrier layer and the conductive layer with the composition according to any one of claims 1 to 12 to etch a portion of the barrier layer and a portion of the conductive layer.

19. The method according to claim 18, The barrier layer comprises titanium nitride, titanium oxynitride, or any combination thereof. The titanium nitride and the titanium oxynitride each optionally further comprise indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof, and The conductive layer comprises tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

20. The method of claim 18, further comprising: After forming the gate electrode by contacting the barrier layer and the conductive layer with the composition to etch a portion of the barrier layer and a portion of the conductive layer to form an etched barrier layer and an etched conductive layer, an insulating layer is provided on the surface of the etched barrier layer and the surface of the etched conductive layer.

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