Composition, method of treating metal-containing layer and method of manufacturing electronic device

Abstract

A composition comprising an oxidizing agent, phosphoric acid, an organic acid, and an etching control agent, wherein the oxidizing agent comprises hydrogen peroxide and an iodine-containing compound, and the etching control agent comprises a nitrogen-containing compound, and having a pH of less than 1, a method for treating a metal-containing film using the same, and a method for manufacturing an electronic device using the same are provided.

Description

Technology Field

[0001] The invention relates to a composition, a method for treating a metal-containing film using the same, and a method for manufacturing an electronic device using the same. Background Technology

[0002] To meet the demands for superior performance and low prices from consumers, there is a need for increased integration density and improved reliability of various electronic devices, such as semiconductor devices. As the integration density of semiconductor devices increases, damage to the components during the manufacturing process has a greater impact on the reliability and electrical characteristics of the devices. In particular, during the manufacturing process of semiconductor devices, various processing steps, such as etching, cleaning, and polishing, may be performed on specific films (e.g., metal-containing films). Consequently, there is a continuous demand for compositions with appropriate etching rates to effectively perform these metal-containing film processing steps. The problem to be solved

[0003] The present invention provides a composition capable of effectively controlling the etching rate of various metal-containing films, a method for processing metal-containing films using the same, and a method for manufacturing electronic devices using the same. means of solving the problem

[0004] According to one aspect, a composition is provided comprising an oxidizing agent, a phosphoric acid, an organic acid, and an etching controller, wherein the oxidizing agent comprises hydrogen peroxide and an iodine-containing compound, the etching controller comprises a nitrogen-containing compound, and has a pH of less than 1.

[0005] According to another aspect,

[0006] A step of preparing a substrate provided with a metal-containing film including a first region and a second region; and

[0007] A step of contacting the metal-containing film with the composition;

[0008] Includes,

[0009] The first region and the second region independently comprise 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,

[0010] A metal-containing film treatment method is provided in which the material included in the first region and the material included in the second region are different from each other.

[0011] According to another aspect, as a method for manufacturing electronic devices including transistors,

[0012] The above transistor is,

[0013] channel;

[0014] A source and a drain electrically connected to the above channel and spaced apart from each other; and

[0015] Gate electrode;

[0016] A gate insulating film disposed between the gate electrode and the channel;

[0017] Includes,

[0018] The step of providing the gate electrode is,

[0019] A step of providing a barrier layer comprising a metal nitride, a metal oxide nitride, or a combination thereof;

[0020] A step of providing a conductive layer including a conductive metal; and

[0021] A step of 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 a gate electrode;

[0022] A method for manufacturing an electronic device, including, is provided. Effects of the invention

[0023] The above composition facilitates easy control of the etching rate for various metal-containing films, and can be effectively used in various processing processes for the metal-containing films, such as etching, cleaning, and polishing processes. Therefore, by processing the metal-containing film using the above composition, high-quality electronic devices and / or electronic apparatuses can be manufactured. Brief explanation of the drawing

[0024] FIGS. 1a and 2 are drawings briefly illustrating an embodiment of a metal-containing film treatment method, and FIG. 1b is a drawing briefly illustrating the surface of the metal-containing film (20A) of FIG. 1a that can come into contact with the composition (30). Figures 3 and 4 are diagrams briefly illustrating other embodiments of a metal-containing film treatment method. FIG. 5 is a schematic plan view of an electronic device according to an exemplary embodiment. FIG. 6a is a perspective view of one embodiment of the electronic device shown in FIG. 5. FIG. 6b is a perspective view of another embodiment of the electronic device shown in FIG. 5. FIGS. 7 to 9 are drawings briefly illustrating part of the manufacturing process of the transistor structure shown in FIG. 6a. FIG. 10 is a process flow diagram of one embodiment of an electronic device manufacturing method. Figure 11a is a photograph of the surface of a molybdenum film obtained after immersion in the composition of Example 1. Figure 11b is a photograph of the surface of a molybdenum film obtained after immersion in the composition of Comparative Example C1. Figure 12 is a photograph of the surface of a molybdenum film obtained after immersion in the composition of Example 11. Specific details for implementing the invention

[0025] metal-containing film

[0026] The above metal-containing film is an alkali metal (e.g., sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), etc.), an alkaline earth metal (e.g., beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), etc.), a lanthanide metal (e.g., lanthanum (La), europium (Eu), terbium (Tb), ytterbium (Yb), etc.), a transition metal (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), It may include silver (Ag), zinc (Zn, etc.), post-transition metals (e.g., aluminum (Al), gallium (Ga), indium (In), thallium (Tl), tin (Sn), bismuth (Bi), etc.), or any combination thereof.

[0027] According to one embodiment, the metal-containing film may comprise 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.

[0028] According to another embodiment, the metal-containing film may include two or more different metals.

[0029] According to another embodiment, the metal-containing film may include titanium.

[0030] According to another embodiment, the metal-containing film comprises i) titanium (Ti) and ii) optionally further comprises, in addition to titanium, 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.

[0031] The metal-containing film may comprise a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.

[0032] According to one embodiment, the metal-containing film comprises a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof, and each of the metal, the metal of the metal nitride, the metal of the metal oxide, and the metal of the metal oxynitride may comprise 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.

[0033] According to another embodiment, the metal-containing film may include a metal nitride, a metal oxynitride, or a combination thereof as described above (e.g., titanium nitride, titanium oxynitride, or a combination thereof).

[0034] According to another embodiment, the metal-containing film may include a metal as described above (e.g., a conductive metal such as tungsten, molybdenum, ruthenium, etc.).

[0035] According to another embodiment, the metal-containing film may comprise i) a metal nitride, metal oxynitride, or a combination thereof as described above (e.g., titanium nitride, titanium oxynitride, or a combination thereof) and ii) a conductive metal (e.g., a conductive metal such as tungsten, molybdenum, ruthenium, etc.).

[0036] According to another embodiment, the metal-containing film comprises titanium nitride, titanium oxide nitride, or a combination thereof, and in addition to titanium nitride, titanium oxide nitride, or a combination thereof, may further comprise tungsten, molybdenum, ruthenium, or any combination thereof. Each of the titanium nitride and titanium oxide nitride may optionally further comprise indium, aluminum, lanthanum, scandium, gallium, silicon, or any combination thereof.

[0037] According to another embodiment, the metal-containing film may include titanium nitride, titanium nitride containing aluminum (e.g., TiAlN), titanium nitride containing lanthanum, titanium nitride containing silicon (e.g., TiSiN), etc.

[0038] The metal-containing film may be a single-layer structure comprising one or more materials or a multilayer structure comprising different materials. A plurality of films included in the multilayer structure may be stacked vertically or arranged horizontally with respect to a substrate. The single-layer structure and the multilayer structure may have various three-dimensional patterns (e.g., via holes, trenches, etc.).

[0039] According to one embodiment, the metal-containing film comprises a first region and a second region, and the first region and the second region independently comprise 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 and the material included in the second region may be different from each other.

[0040] According to another embodiment, the first region may include titanium.

[0041] According to another embodiment, the first region comprises i) titanium (Ti), and ii) in addition to titanium, may optionally further comprise 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.

[0042] According to another embodiment, the second region may include tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

[0043] In another embodiment, the first region may comprise titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), or any combination thereof, and the second region may comprise tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

[0044] According to another embodiment, the first region comprises a metal nitride, a metal oxide nitride, or a combination thereof, and the second region may comprise a conductive metal.

[0045] 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.

[0046] According to another embodiment, the first region comprises titanium nitride, titanium oxide nitride, or a combination thereof, and each of the titanium nitride and titanium oxide nitride may optionally further comprise indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

[0047] According to another embodiment, the first region may include titanium nitride, titanium nitride further containing aluminum (e.g., TiAlN), titanium nitride further containing lanthanum, titanium nitride further containing silicon (e.g., TiSiN), etc.

[0048] In this specification, the statement that any film is etched may mean that some or more of the materials constituting the film are removed.

[0049] composition

[0050] The above composition may include an oxidizing agent, phosphoric acid, an organic acid, and an etching controller.

[0051] The above composition can be used in various processing processes for metal-containing films described in this specification, such as etching, cleaning, polishing, etc.

[0052] The above composition may further include water.

[0053] According to one embodiment, the composition may not contain a fluorine-containing compound. Although not intended to be limited by any specific theory, if the composition contains a fluorine-containing compound, when the metal-containing film is treated using the composition, adjacent materials disposed adjacent to the metal-containing film as described below, such as various oxides, may be damaged, thereby causing a degradation in the performance of electronic devices and / or semiconductor devices.

[0054] Oxidizing agent

[0055] Oxidizing agents serve to etch more than a portion of the metal-containing film and may include hydrogen peroxide and an iodine-containing compound.

[0056] According to one embodiment, the iodine-containing compound may include iodine, periodic acid (H5IO6), iodic acid (HIO3), or any combination thereof.

[0057] According to another embodiment, the oxidizing agent may include hydrogen peroxide and iodic acid.

[0058] According to another embodiment, the oxidizing agent may include hydrogen peroxide and periodic acid.

[0059] According to another embodiment, the composition may not include a fluorine-containing compound (e.g., HF, NH4F, etc.) as an oxidizing agent. Although not intended to be limited by any specific theory, if the composition includes a fluorine-containing compound as an oxidizing agent, when the metal-containing film is treated using the composition, adjacent materials disposed adjacent to the metal-containing film, such as various oxides, as described below, may be damaged, which may result in a degradation of the performance of electronic devices and / or semiconductor devices.

[0060] The content (weight) of the above oxidizing agent is, for example, per 100 wt% of the composition, 0.001 wt% to 10 wt%, 0.001 wt% to 7 wt%, 0.001 wt% to 5 wt%, 0.001 wt% to 3 wt%, 0.001 wt% to 1 wt%, 0.001 wt% to 0.7 wt%, 0.005 wt% to 10 wt%, 0.005 wt% to 7 wt%, 0.005 wt% to 5 wt%, 0.005 wt% to 3 wt%, 0.005 wt% to 1 wt%, 0.005 wt% to 0.7 wt%, 0.01 wt% to 10 wt%, 0.01 wt% to 7 wt%, 0.01 wt% to 5 wt%, 0.01 wt% to 3 wt%, 0.01 wt% to 1 wt%, 0.01 wt% to 0.7 wt%, 0.05 wt% to 10 wt%, 0.05 wt% to 7 wt%, 0.05 wt% to 5 wt%, 0.05 wt% to 3 wt%, 0.05 wt% to 1 wt%, 0.05 wt% to 0.7 wt%, 0.1 wt% to 10 wt%, 0.1 wt% to 7 wt%, 0.1 wt% to 5 wt%, 0.1 wt% to 3 wt%, 0.1 wt% to 1 wt%, 0.1 wt% to 0.7 It may be wt%, 0.3 wt% to 10 wt%, 0.3 wt% to 7 wt%, 0.3 wt% to 5 wt%, 0.3 wt% to 3 wt%, 0.3 wt% to 1 wt%, or 0.3 wt% to 0.7 wt%.

[0061] The weight ratio of the iodine-containing compound to the hydrogen peroxide may be 1:10 to 1:100, 1:10 to 1:50, or 1:15 to 1:30.

[0062] The content (weight) of the above hydrogen peroxide is, for example, per 100 wt% of the composition, 0.01 wt% to 10 wt%, 0.01 wt% to 7 wt%, 0.01 wt% to 5 wt%, 0.01 wt% to 3 wt%, 0.01 wt% to 1 wt%, 0.01 wt% to 0.7 wt%, 0.05 wt% to 10 wt%, 0.05 wt% to 7 wt%, 0.05 wt% to 5 wt%, 0.05 wt% to 3 wt%, 0.05 wt% to 1 wt%, 0.05 wt% to 0.7 wt%, 0.1 wt% to 10 wt%, 0.1 wt% to 7 wt%, 0.1 It may be wt% to 5 wt%, 0.1 wt% to 3 wt%, 0.1 wt% to 1 wt%, 0.1 wt% to 0.7 wt%, 0.3 wt% to 10 wt%, 0.3 wt% to 7 wt%, 0.3 wt% to 5 wt%, 0.3 wt% to 3 wt%, 0.3 wt% to 1 wt%, or 0.3 wt% to 0.7 wt%.

[0063] The content (weight) of the iodine-containing compound above may be, for example, 0.001 wt% to 5 wt%, 0.001 wt% to 3 wt%, 0.001 wt% to 1 wt%, 0.001 wt% to 0.5 wt%, 0.005 wt% to 5 wt%, 0.005 wt% to 3 wt%, 0.005 wt% to 1 wt%, 0.005 wt% to 0.5 wt%, 0.01 wt% to 5 wt%, 0.01 wt% to 3 wt%, 0.01 wt% to 1 wt%, or 0.01 wt% to 0.5 wt% per 100 wt% of the composition.

[0064] Phosphoric acid

[0065] The above phosphoric acid, together with the above oxidizing agent, can play a role in etching more than a portion of the metal-containing film.

[0066] According to one embodiment, the composition may not contain sulfuric acid, hydrochloric acid, and nitric acid. Although not intended to be limited by any specific theory, if sulfuric acid, hydrochloric acid, or nitric acid is used together with an oxidizing agent as described above, the stability of the composition may be reduced, making it unsuitable for use in a metal-containing film treatment process.

[0067] The content (weight) of the above phosphoric acid is, for example, per 100 wt% of the composition, 10 wt% to 85 wt%, 15 wt% to 85 wt%, 20 wt% to 85 wt%, 25 wt% to 85 wt%, 30 wt% to 85 wt%, 35 wt% to 85 wt%, 40 wt% to 85 wt%, 45 wt% to 85 wt%, 50 wt% to 85 wt%, 55 wt% to 85 wt%, 10 wt% to 80 wt%, 15 wt% to 80 wt%, 20 wt% to 80 wt%, 25 wt% to 80 wt%, 30 wt% to 80 wt%, 35 wt% to 80 wt%, 40 wt% to 80 wt%, 45 wt% to 80 wt%, 50 wt% to 80 wt%, 55 wt% to 80 wt%, 10 wt% to 75 wt%, 15 wt% to 75 wt%, 20 wt% to 75 wt%, 25 wt% to 75 wt%, 30 wt% to 75 wt%, 35 wt% to 75 wt%, 40 wt% to 75 wt%, 45 wt% to 75 wt%, 50 wt% to 75 wt%, 55 wt% to 75 wt%, 10 wt% to 70 wt%, 15 wt% to 70 wt%, 20 wt% to 70 wt%, 25 It may be wt% to 70 wt%, 30 wt% to 70 wt%, 35 wt% to 70 wt%, 40 wt% to 70 wt%, 45 wt% to 70 wt%, 50 wt% to 70 wt%, 55 wt% to 70 wt%, 10 wt% to 65 wt%, 15 wt% to 65 wt%, 20 wt% to 65 wt%, 25 wt% to 65 wt%, 30 wt% to 65 wt%, 35 wt% to 65 wt%, 40 wt% to 65 wt%, 45 wt% to 65 wt%, 50 wt% to 65 wt%, or 55 wt% to 65 wt%.

[0068] organic acids

[0069] The above organic acid can play a role in controlling the etching rate of more than a portion of the metal-containing film.

[0070] The above organic acid may include a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, or any combination thereof.

[0071] The number of carbon atoms included in each of the monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid may be 1 to 31, 1 to 20, or 1 to 10.

[0072] According to one embodiment, the organic acid is,

[0073] HCOOH;

[0074] An aliphatic compound having 1 to 30 carbon atoms (e.g., 1 to 20 or 1 to 15 carbon atoms) substituted with at least one carboxylic acid (*-COOH) (e.g., 1, 2, or 3 carboxylic acids), or an aromatic compound having 6 to 30 carbon atoms (e.g., 6 to 15 or 6 to 10 carbon atoms); or

[0075] Any combination of these;

[0076] Includes,

[0077] At least one hydrogen of the aliphatic compound and the aromatic compound is optionally a hydroxyl group, a thiol group, an amino group, or a C1-C 10 Alkyl groups (e.g., C1-C5 alkyl groups), C1-C 10 Alkoxy groups (e.g., C1-C5 alkoxy groups), C1-C 10 Alkylthio group (e.g., C1-C5 alkylthio group), di(C1-C 10It may be additionally substituted with an alkyl)amino group (e.g., a di(C1-C5 alkyl)amino group), a phenyl group, or any combination thereof.

[0078] According to one embodiment, the aliphatic compound may be a saturated aliphatic compound (e.g., alkane, cycloalkane, etc.) or an unsaturated aliphatic compound (e.g., alkene, alkyne, cycloalkene, etc.).

[0079] According to another embodiment, the aliphatic compound may be an acyclic aliphatic compound (e.g., alkanes, alkenes, alkynes, etc.) or a cyclic aliphatic compound (e.g., cycloalkanes, cycloalkenes, adamantanes, norbornanes, etc.).

[0080] According to another embodiment, the aliphatic compound may be a straight-chain aliphatic compound (e.g., CH3-CH2-CH2-CH2-CH3) or a branched-chain aliphatic compound (e.g., CH3-CH(CH3)-CH2-CH3, CH3-C(CH3)2-CH3).

[0081] According to another embodiment, the aromatic compound may be benzene.

[0082] According to another embodiment, the organic acid may include formic acid, acetic acid, propionic acid, butyric acid, valeic 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.

[0083] The content of the above organic acid may be 0.1 wt% to 15 wt%, 0.5 wt% to 15 wt%, 1 wt% to 15 wt%, 3 wt% to 15 wt%, 5 wt% to 15 wt%, 7 wt% to 15 wt%, 0.1 wt% to 13 wt%, 0.5 wt% to 13 wt%, 1 wt% to 13 wt%, 3 wt% to 13 wt%, 5 wt% to 13 wt%, or 7 wt% to 13 wt% per 100 wt% of the above composition.

[0084] Etching regulator

[0085] The above etching control agent, together with the above organic acid, can interact with various metal atoms in the metal-containing film to be treated, thereby playing a role in controlling the etching rate, etc.

[0086] The above etching regulator may include a nitrogen-containing compound.

[0087] According to one embodiment, the nitrogen-containing compound may not contain a hydroxyl group.

[0088] According to another embodiment, the etching control agent may comprise a hydroxyl-free and nitrogen-containing compound. In this specification, the term "hydroxyl-free and nitrogen-containing compound" means a compound that does not contain a hydroxyl group and contains at least one nitrogen as a molecular constituent atom.

[0089] According to another embodiment, the nitrogen-containing compound may include an amine-containing alcohol, an amine-containing acid, a polyalkylene polyamine (e.g., a compound represented by the following chemical formula 5), ​​a cyclic group-containing amine (e.g., a compound represented by the following chemical formula 6), a polymer having a nitrogen-containing repeating unit, or a combination thereof.

[0090] According to another embodiment, the nitrogen-containing compound may include a compound represented by the following chemical formula 5, a compound represented by the following chemical formula 6, or a combination thereof:

[0091] <Chemical Formula 5>

[0092] T 52 -[(L5) a5 ]-T 51

[0093] <Chemical Formula 6>

[0094] CY6-[L6-N(R 61 )(R 62 )] a6

[0095] In the above chemical formula 5, L5 is *-C(Z 51 )(Z52 )-*', *-N(Z 53 )-*', *-C(=O)-*' or *-O-*' and,

[0096] In the above chemical formula 5, a5 is an integer from 1 to 30, and

[0097] T in the above chemical formula 5 51 is *-N(R 51 )(R 52 ) and,

[0098] T in the above chemical formula 5 52 is *-N(R 53 )(R 54 ), *-OH, *-SH, or *-C(=O)-OH, and

[0099] In the above chemical formula 6, the ring CY6 is a carbocyclic group having 5 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, and

[0100] In the above chemical formula 6, L6 is a single bond or C1-C 30 It is an alkylene group, and

[0101] In the above chemical formula 6, a6 is an integer from 1 to 5, and

[0102] Z in the above chemical formulas 5 and 6 51 , Z 52 , Z 53 , R 51 , R 52 , R 53 , R 54 , R 61 and R 62 are independently of each other,

[0103] Hydrogen, amino group, *-OH, *-SH, or *-C(=O)-OH; or

[0104] amino group, di(C1-C 30 Alkyl)amino group, *-C(=O)-N(Q 51 )(Q 52 ), *-OH, *-SH, *-C(=O)-OH, or any combination thereof, substituted or unsubstituted, C1-C 30 Alkyl group;

[0105] And,

[0106] Q 51 and Q 52 are independently of each other,

[0107] Hydrogen; or

[0108] amino group, di(C1-C 30 Substituted or unsubstituted with an alkyl)amino group, or a combination thereof, C1-C 30 Alkyl group;

[0109] And,

[0110] * and *' are each bonding sites with neighboring atoms.

[0111] According to another embodiment, each L5 in the above chemical formula 5 is *-C(Z 51 )(Z 52 )-*'can be.

[0112] According to another embodiment, each L5 in the above chemical formula 5 is *-C(Z 51 )(Z 52 It can be )-*', *-C(=O)-*' or *-O-*'.

[0113] According to another embodiment, each L5 in the above chemical formula 5 is *-C(Z 51 )(Z 52 )-*' or *-N(Z 53 )-*'can be.

[0114] According to another embodiment, each L5 in the above chemical formula 5 is *-C(Z 51 )(Z 52 )-*' or *-N(Z 53 )-*', but at least one L5 is *-N(Z 53 )-*'can be.

[0115] According to another embodiment, a5 in the above chemical formula 5 may be an integer from 1 to 25, an integer from 1 to 20, an integer from 1 to 15, an integer from 1 to 11, an integer from 2 to 25, an integer from 2 to 20, an integer from 2 to 15, or an integer from 2 to 11.

[0116] According to another embodiment, each L5 in the above chemical formula 5 is *-C(Z 51 )(Z 52 )-*' and a5 can be an integer from 1 to 11 or from 2 to 11.

[0117] According to another embodiment, each L5 in the above chemical formula 5 is *-C(Z 51 )(Z 52 )-*', *-C(=O)-*' or *-O-*', and a5 can be an integer from 2 to 11.

[0118] According to another embodiment, each L5 in the above chemical formula 5 is *-C(Z 51 )(Z 52 )-*' or *-N(Z 53 )-*' and a5 can be an integer from 5 to 11.

[0119] According to another embodiment, each L5 in the above chemical formula 5 is *-C(Z 51 )(Z 52 )-*' or *-N(Z 53 )-*' and, *-N(Z 53 The number of )-*' can be 1, 2, 3, or 4.

[0120] According to another embodiment, T of Chemical Formula 5 above 52 is *-N(R 53 )(R 54 It can be.

[0121] According to another embodiment, T in the above chemical formula 5 52 It can be *-OH or *-C(=O)-OH.

[0122] According to another embodiment, the ring CY6 in the formula 6 may be a saturated or unsaturated carbocyclic group having 5 to 15 carbon atoms or 5 to 10 carbon atoms, or a saturated or unsaturated heterocyclic group having 2 to 15 carbon atoms or 2 to 10 carbon atoms.

[0123] According to another embodiment, the ring CY6 in the formula 6 comprises a cyclopentane group, a cyclohexane group, a cycloheptane group, a cyclooctane group, a cyclopentene group, a cyclohexene group, a cycloheptene group, a cyclooctene group, a benzene group, a naphthalene group, a piperazine group, a pyrrolidine group, a piperidine group, an azepane group, a tetrahydrofuran group, a tetrahydrothiophene group, a tetrahydro-2H-pyran group, a tetrahydro-2H-thiopyran group, a pyrazol group, an imidazole group, a triazole group, a 4H-pyran-4-one group, and a pyridine group. It may be a group, pyrimidine group, pyrazine group, pyridazine group, triazine group, carbazole group, dibenzofuran group, or dibenzothiophene group.

[0124] According to another embodiment, L6 in Formula 6 is a single bond or C1-C 10 It may be an alkylene group (e.g., a C1-C5 alkylene group).

[0125] According to another embodiment, a6 in the above chemical formula 6 may be 1 or 2.

[0126] According to another embodiment, Z in the above chemical formulas 5 and 6 51 , Z 52 , Z 53 , R 51 , R 52 , R 53 , R 54 , R 61 and R 62 are independently of each other,

[0127] Hydrogen or amino group; or

[0128] amino group, di(C1-C 30 Alkyl)amino group, *-C(=O)-N(Q51 )(Q 52 ), or substituted or unsubstituted by any combination thereof, C1-C 30 Alkyl group;

[0129] And,

[0130] Q 51 and Q 52 are independently of each other,

[0131] Hydrogen; or

[0132] amino group, di(C1-C 30 Substituted or unsubstituted with an alkyl)amino group, or a combination thereof, C1-C 30 Alkyl group;

[0133] It could be.

[0134] According to another embodiment, Z in the above chemical formulas 5 and 6 51 , Z 52 , Z 53 , R 51 , R 52 , R 53 , R 54 , R 61 and R 62 are independently of each other,

[0135] Hydrogen or amino group; or

[0136] amino group, di(C1-C 10 Alkyl)amino group, *-C(=O)-N(Q 51 )(Q 52 ), or substituted or unsubstituted by any combination thereof, C1-C 10 Alkyl group;

[0137] And,

[0138] Q 51 and Q 52 are independently of each other,

[0139] Hydrogen; or

[0140] amino group, di(C1-C 10 Substituted or unsubstituted with an alkyl)amino group, or a combination thereof, C1-C 10 Alkyl group;

[0141] It could be.

[0142] According to another embodiment, the nitrogen-containing compound may include a compound represented by the following chemical formula 51:

[0143] <Chemical Formula 51>

[0144] T 52 -{[C(Z 51 )(Z 52 )] a51 -N(Z 53 )} b51 -[C(Z 54 )(Z 55 )] a52 -T 51

[0145] Among the above chemical formula 51,

[0146] T 51 , T 52 , Z 51 , Z 52 and Z 53 The description for each is the same as that described in this specification, and

[0147] Z 54 and Z 55 The descriptions for each of the following are Z in this specification. 51 It is identical to the explanation for,

[0148] a51 and a52 are independently integers from 2 to 5 (e.g., 2 or 3), and

[0149] b51 is an integer from 1 to 7 (e.g., 1, 2, or 3).

[0150] According to another embodiment, the nitrogen-containing compound may include at least one of the following compounds A1 to A32:

[0151]

[0152]

[0153]

[0154] According to another embodiment, the nitrogen-containing compound may comprise a polymer having a nitrogen-containing repeating unit (e.g., a polymer having a hydroxyl-free and nitrogen-containing repeating unit). The polymer may be a water-soluble polymer. As another example, the polymer may be a homopolymer.

[0155] According to another embodiment, the nitrogen-containing compound may include a polyallylamine-based polymer (e.g., a hydroxyl group-free polyarylamine-based polymer).

[0156] The above nitrogen-containing repeating unit may include a repeating unit represented by the following chemical formula 1-1, a repeating unit represented by the following chemical formula 1-2, a repeating unit represented by the following chemical formula 1-3, a repeating unit represented by the following chemical formula 1-4, or any combination thereof:

[0157]

[0158] In chemical formulas 1-1 to 1-3, A1 is *-C(R 16 )(R 17 )-*', *-N(R 16 It can be )-*', *-C(=O)-*', *-O-*', or *-S-*'.

[0159] In chemical formulas 1-1 to 1-3, a1 is an integer from 0 to 20, and if a1 is 2 or more, the 2 or more A1s may be identical or different from each other. If a1 is 0, *-(A1) a1 -*' becomes a single combination.

[0160] According to one embodiment, the above a1 may be 0.

[0161] According to another embodiment, the above a1 may not be 0.

[0162] According to another embodiment, the a1 may be an integer from 0 to 10.

[0163] According to another embodiment, the a1 may be an integer from 1 to 5.

[0164] In chemical formulas 1-1 to 1-4, b1 is an integer from 0 to 10, and if b1 is 2 or more, then 2 or more *-C(R 14 )(R 15 )-*' may be identical or different. If the above b1 is 0, *-C(R 14 )(R 15 )-*' becomes a single combination.

[0165] According to one embodiment, b1 may be an integer from 0 to 5.

[0166] In chemical formulas 1-1 to 1-3, T1 is *-N(Z 11 )(Z 12 ), *-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - , may be a group represented by the following chemical formula AN or a group represented by the following chemical formula BN:

[0167]

[0168] Among the above chemical formulas 1-3, 1-4, AN and BN, ring CY1 to ring CY4 may independently be cyclic groups having 2 to 10 carbon atoms.

[0169] According to one embodiment, T1 in chemical formulas 1-1 to 1-3 is *-N(Z 11 )(Z 12 ) or *-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - Igo, Z 11 To Z 13 Each can be hydrogen.

[0170] According to another embodiment, T1 in the above chemical formulas 1-1 to 1-3 is *-N(Z 11 )(Z 12 ) or *-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - Igo, Z 11 is hydrogen, and Z 12 It may not be hydrogen.

[0171] According to another embodiment, T1 in the above chemical formulas 1-1 to 1-3 is *-N(Z 11 )(Z 12 ) or *-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - Igo, Z 11 and Z 12 Each one may not be hydrogen.

[0172] According to another embodiment, T1 in the above chemical formulas 1-1 to 1-3 is *-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - Igo, Z 11 To Z 13 Each one may not be hydrogen.

[0173] According to another embodiment, T1 in the above formulas 1-1 to 1-3 is a group represented by the above formula AN, and Z in T2 of the above formula AN 11 and Z 12 It can be hydrogen.

[0174] According to another embodiment, T1 in the above formulas 1-1 to 1-3 is a group represented by the above formula AN, and Z in T2 of the above formula AN 11 It may not be hydrogen.

[0175] According to another embodiment, T1 among the formulas 1-1 to 1-3 is the group represented by the formula AN, and T2 among the formula AN is *-[N(Z 11 )(Z 12 )] + [Z 14 ] - -*' and, Z 11 and Z 12 Each one may not be hydrogen.

[0176] According to another embodiment, T2 of the above chemical formula 1-4, Z 11 and Z 12 It can be hydrogen.

[0177] According to another embodiment, T2 of the above chemical formula 1-4, Z 11 It is not hydrogen, Z 12 It can be hydrogen.

[0178] According to another embodiment, T2 in the above chemical formula 1-4 is *-[N(Z 11 )(Z 12 )] + [Z 14 ] - -*' and, Z 11 and Z 12 Each one may not be hydrogen.

[0179] Among the above chemical formulas 1-3, 1-4, AN and BN, c1 represents the number of R1 and can be selected from integers from 0 to 10. If c1 is 2 or more, the 2 or more R1s may be the same or different from each other.

[0180] In the above chemical formulas 1-4 and AN, T2 is *-N(Z 11 )-*' or *-[N(Z 11 )(Z 12 )] + [Z 14 ] - -*'It could be. Z 11 , Z 12 and Z 14 For descriptions of each, refer to those set forth in this specification.

[0181] According to another embodiment, CY1 in the above chemical formula 1-3 may be a cyclopropane group, a cyclobutane group, a cyclopentane group, a cyclohexane group, a cycloheptane group, a cyclooctane group, an oxirane group, an oxetane group, a tetrahydrofuran group, or a tetrahydropyran group.

[0182] According to another embodiment, the ring CY2 in the above chemical formula 1-4 may be a saturated cyclic group having 4, 5, 6, or 7 carbon atoms.

[0183] According to another embodiment, among the above chemical formula AN,

[0184] i) T2 is *-N(Z 11 )-*' and the ring CY3 is a pyrrole group, an imidazole group, a pyrazole group, an aziridine group, an azetidine group, a pyrrolidine group, or a piperidine group, or

[0185] ii) T2 is *-[N(Z 11 )(Z 12 )] + [Z 14 ] - -*' and the ring CY3 can be a saturated cyclic group with 4, 5, 6 or 7 carbon atoms.

[0186] According to another embodiment, the ring CY4 in the chemical formula BN may be a pyrrole group, an imidazole group, a pyrazole group, an aziridine group, an azetidine group, a pyrrolidine group, or a piperidine group.

[0187] The above R1, R 11 to R 17 and Z 11 To Z 13 are independently of each other,

[0188] Hydrogen, *-F, *-Cl, *-Br, *-I, *-SH, *-C(=O)-Q1, *-NH-C(=O)-Q1, *-C(=O)-O-Q1, *-SO2-Q1, *-P(=O)-(Q1)(Q2), *-N(Q1)(Q2), or *-[N(Q1)(Q2)(Q3)] + [Q4]; or

[0189] *-F, *-Cl, *-Br, *-I, *-SH, *-C(=O)-Q 11 , *-NH-C(=O)-Q 11 , *-C(=O)-OQ 11 , *-SO2-Q 11 , *-P(=O)-(Q 11 )(Q 12 ), *-N(Q 11 )(Q 12 ), *-[N(Q 11 )(Q 12 )(Q 13 )] + [Q 14 ], C1-C 30 Alkyl group, C1-C 30 Alkoxy group, C2-C 30 alkenyl group, C3-C 30 Carbocyclic group, C1-C 30 C1-C, substituted or unsubstituted with heterocyclic groups, or any combination thereof 30 Alkyl group, C1-C 30 Alkoxy group, C2-C 30 alkenyl group, C3-C 30 Carbocyclic group, or C1-C 30 Heterocyclic group;

[0190] It could be.

[0191] The above n1 and n2 may be integers from 1 to 20 independently of each other.

[0192] The above R1, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17, Z 11 , Z 12 and Z 13 Two or more of them can optionally combine to form a cyclic group having 2 to 10 carbon atoms, and

[0193] The above Q1 to Q3 and Q 11 to Q 13 are independently of each other,

[0194] Hydrogen, *-F, *-Cl, *-Br, *-I, *-SH, *-C(=O)-H, *-C(=O)-NH2, *-C(=O)-NH(CH3), *-C(=O)-N(CH3)2, *-NH-C(=O)-NH2, *-NH-C(=O)-NH(CH3), *-NH-C(=O)-N(CH3)2, *-NH2, *-NH(CH3) or *-N(CH3)2; or

[0195] *-F, *-Cl, *-Br, *-I, *-SH, *-C(=O)-H, *-C(=O)-NH2, *-C(=O)-NH(CH3), *-C(=O)-N(CH3)2, *-NH-C(=O)-NH2, *-NH-C(=O)-NH(CH3), *-NH-C(=O)-N(CH3)2, *-NH2, *-NH(CH3), *-N(CH3)2, C1-C 30 Alkyl group, C1-C 30 Alkoxy group, C2-C 30 alkenyl group, C3-C 30 Carbocyclic group, C1-C 30 C1-C, substituted or unsubstituted with heterocyclic groups, or any combination thereof 30 Alkyl group, C1-C 30 Alkoxy group, C2-C 30 alkenyl group, C3-C 30 Carbocyclic group, or C1-C 30 Heterocyclic group;

[0196] It could be.

[0197] The above C3-C 30The carbocyclic group may be, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a phenyl group, a naphthyl group, etc.

[0198] The above C1-C 30 The heterocyclic group may be, for example, an oxiranyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, a pyridinyl group, a pyrimidinyl group, etc.

[0199] Above [Z 14 ] - , [Q4] - and [Q 14 ] - Each can be a negative ion.

[0200] For example, the above [Z 14 ] - , [Q4] - and [Q 14 ] - are independently of each other, borate ([B(OH)4] - ), fluoride([F] - ), chloride([Cl] - ), bromide([Br] - ), iodide([I] - ), hydrogen sulfate ([HSO4] - ), nitrate ([NO3] - ), formate ([HCOO] - ), acetate ([CH3COO] - ), or dihydrogen phosphate ([H2PO4] - It can be.

[0201] In this specification, * and *' each are bonding sites with neighboring atoms unless otherwise defined.

[0202] According to one embodiment, the repeating unit represented by the formula 1-3 may be a repeating unit represented by any one of the following formulas 1-3(1) to 1-3(8):

[0203]

[0204] Among the above chemical formulas 1-3(1) to 1-3(8),

[0205] A1, a1, b1, T1, R1, R 14 and R 15 The descriptions for each are the same as those described in this specification, and

[0206] c11 is 0 or 1, and

[0207] c13 is an integer from 0 to 3, and

[0208] c15 is an integer from 0 to 5, and

[0209] c17 is an integer from 0 to 7, and

[0210] c19 is an integer from 0 to 9, and

[0211] * and *' are each bonding sites with neighboring atoms.

[0212] According to another embodiment, the repeating unit represented by the above chemical formula 1-4 may be a repeating unit represented by any one of the following chemical formulas 1-4(1) to 1-4(3):

[0213]

[0214] Among the above chemical formulas 1-4(1) to 1-4(3),

[0215] b1, R1, R 14 , R 15 The descriptions for and T2 are each the same as those described in this specification, and

[0216] c16 is an integer from 0 to 6, and

[0217] c18 is an integer from 0 to 8, and

[0218] * and *' are each bonding sites with neighboring atoms.

[0219] According to another embodiment, the group represented by the chemical formula AN may be a group represented by one of the following chemical formulas AN (1) to AN (12):

[0220]

[0221] Among the above chemical formulas AN(1) to AN(12),

[0222] The descriptions of R1 and T2 are each the same as those described in this specification, and

[0223] c12 is an integer from 0 to 2, and

[0224] c13 is an integer from 0 to 3, and

[0225] c16 is an integer from 0 to 6, and

[0226] c18 is an integer from 0 to 8, and

[0227] * is a bonding site with a neighboring atom.

[0228] According to another embodiment, the group represented by the chemical formula BN may be a group represented by one of the following chemical formulas BN (1) to BN (7):

[0229]

[0230] Among the above chemical formulas BN(1) to BN(7),

[0231] The description of R1 is the same as that described in this specification, and

[0232] c13 is an integer from 0 to 4, and

[0233] c14 is an integer from 0 to 4, and

[0234] c16 is an integer from 0 to 6, and

[0235] c18 is an integer from 0 to 8, and

[0236] c20 is an integer from 0 to 10, and

[0237] * is a bonding site with a neighboring atom.

[0238] According to another embodiment, the nitrogen-containing repeating unit comprises a repeating unit represented by Chemical Formula 1-1, wherein A1 is *-C(R 16 )(R17 )-*' and a1 is an integer from 1 to 5, b1 is an integer from 0 to 5, and T1 is *-N(Z 11 )(Z 12 ) or *-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - and R 11 to R 17 , Z 11 To Z 13 and [Z 14 ] - The description for each may be the same as that described in this specification.

[0239] The weight average molecular weight of the polymer having the above nitrogen-containing repeating unit may be, for example, 200 g / mol to 100,000 g / mol. The weight average molecular weight may be measured, for example, using GPC (gel penetration chromatography) and may be a calculated value using polystyrene.

[0240] According to another embodiment, the polymer having the nitrogen-containing repeating unit may be one of the following polymers 1 to 259:

[0241]

[0242]

[0243] Among the above polymers 1 to 259,

[0244] OMe is a methoxy group, and

[0245] pH is a phenyl group, and

[0246] Ts is a toluenesulfonyl group (*-S(=O)2-(C6H4)-CH3), and

[0247] Ms is a methylsulfonyl group (*-S(=O)2-CH3) and

[0248] n is selected from 2 to 10,000, and

[0249] * and *' are each bonding sites with neighboring atoms.

[0250] The above polymers 1 to 259 may have a weight average molecular weight in the range described in the present specification.

[0251] The content (weight) of the above etching control agent per 100 wt% of the composition is 0.01 wt% to 5 wt%, 0.01 wt% to 4 wt%, 0.01 wt% to 3 wt%, 0.01 wt% to 2 wt%, 0.01 wt% to 1.5 wt%, 0.01 wt% to 1 wt%, 0.05 wt% to 5 wt%, 0.05 wt% to 4 wt%, 0.05 wt% to 3 wt%, 0.05 wt% to 2 wt%, 0.05 wt% to 1.5 wt%, 0.05 wt% to 1 wt%, 0.1 wt% to 5 wt%, 0.1 wt% to 4 wt%, and 0.1 wt% to 3 wt%. It may be wt%, 0.1 wt% to 2 wt%, 0.1 wt% to 1.5 wt%, 0.1 wt% to 1 wt%, 0.5 wt% to 5 wt%, 0.5 wt% to 4 wt%, 0.5 wt% to 3 wt%, 0.5 wt% to 2 wt%, or 0.5 wt% to 1.5 wt%. The content of the etching control agent refers to the content of the solid portion of the polymer when a polymer having nitrogen-containing repeating units is used as the etching control agent.

[0252] The above composition may have a pH of less than 1. For example, the pH of the composition as described above may be less than 1.0, 0.9 or less, 0.7 or less, 0.5 or less, 0.3 or less, 0.1 or less, 0.0 or less, or less than 0.0.

[0253] As another example, the pH of the above composition is -3.0 to 0.9, -3.0 to 0.7, -3.0 to 0.5, -3.0 to 0.3, -3.0 to 0.1, -3.0 to 0.0, -2.5 to 0.9, -2.5 to 0.7, -2.5 to 0.5, -2.5 to 0.3, -2.5 to 0.1, -2.5 to 0.0, -2.0 to 0.9, -2.0 to 0.7, -2.0 to 0.5, -2.0 to 0.3, -2.0 to 0.1, -2.0 to 0.0, -1.5 to 0.9, -1.5 to 0.7, -1.5 to 0.5, -1.5 to 0.3, -1.5 to 0.1, -1.5 to It may be 0.0, -1.0 to 0.9, -1.0 to 0.7, -1.0 to 0.5, -1.0 to 0.3, -1.0 to 0.1, -1.0 to 0.0, -0.5 to 0.9, -0.5 to 0.7, -0.5 to 0.5, -0.5 to 0.3, or -0.5 to 0.1, or -0.5 to 0.0. By having a pH range as described above, the interaction between the etching control agent and the metal atoms in the metal-containing film can be more smoothly achieved.

[0254] According to one embodiment, the composition may comprise 0.001 wt% to 10 wt% of an oxidizing agent, 10 wt% to 70 wt% of phosphoric acid, 0.1 wt% to 15 wt% of an organic acid, and 0.01 wt% to 3 wt% of an etching regulator.

[0255] According to another embodiment, the composition may comprise 0.001 wt% to 5 wt% of an oxidizing agent, 10 wt% to 75 wt% of phosphoric acid, 0.1 wt% to 13 wt% of an organic acid, and 0.01 wt% to 5 wt% of an etching regulator.

[0256] According to another embodiment, the composition may comprise 0.001 wt% to 5 wt% of an oxidizing agent, 10 wt% to 70 wt% of phosphoric acid, 0.1 wt% to 15 wt% of an organic acid, and 0.01 wt% to 5 wt% of an etching regulator.

[0257] According to another embodiment, the composition may be used in a metal-containing film processing process, for example, in etching, cleaning, and polishing processes for a metal-containing film. For a description of the metal-containing film, refer to the description in this specification.

[0258] Alternatively, the above composition may also be used as an etching byproduct remover, a post-etch process byproduct remover, an ashing process byproduct remover, a cleaning composition, a photoresist (PR) remover, an etching composition for a packaging process, a cleaning agent for a packaging process, a wafer adhesive material remover, an etchant, a post-etch residue stripper, an ashing residue cleaner, a photoresist residue stripper, a polishing cleaner (CMP cleaner), or a post-CMP cleaner.

[0259] Metal-containing film treatment method

[0260] By using the composition as described above, a metal-containing film comprising a first region and a second region, wherein the material contained in the first region and the material contained in the second region are different from each other, can be effectively treated. For descriptions of the metal-containing film, the first region, and the second region, respectively, refer to the descriptions provided in this specification.

[0261] According to one embodiment, 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.

[0262] According to another embodiment, the first region may comprise titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), or any combination thereof, and the second region may comprise tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

[0263] According to another embodiment, the first region comprises a metal nitride, a metal oxide nitride, or a combination thereof, and the second region may comprise a conductive metal.

[0264] According to another embodiment, the first region comprises titanium nitride, titanium oxide nitride, or a combination thereof, and each of the titanium nitride and titanium oxide nitride may optionally further comprise indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

[0265] Figures 1a and 2 are diagrams briefly illustrating one embodiment of a metal-containing film treatment method.

[0266] Referring to FIG. 1a, a substrate (10) provided with a metal-containing film (20A) is provided. Although not shown in FIG. 1a, various circuit elements, etc., may be optionally additionally disposed between the substrate (10) and the metal-containing film (20A), for example.

[0267] 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 spaced apart from each other or may be arranged with at least some of them 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 be in contact with the composition (30) so that a portion of the metal-containing film (20A) may be removed. For example, during the etching, cleaning, and / or polishing process of the metal-containing film (20A), the metal-containing film (20A) may be in contact with the composition (30). The description of the composition (30) includes an oxidizing agent, phosphoric acid, an organic acid, and an etching control agent as described in this specification, and a detailed description thereof is to be found in this specification.

[0268] The etching rate ratio, in which the composition (30) etches the first region (21) by dividing the first etching rate by the composition (30) etches the second region (22) by etching the second etching rate, may be 0.009 or higher. For example, the etching ratio in which the composition (30) etches the first region (21) at a first etching rate and the composition (30) etches the second region (22) at a second etching rate may be 0.009 to 1.0, 0.01 to 1.0, 0.011 to 1.0, 0.009 to 0.5, 0.01 to 0.5, 0.011 to 0.5, 0.009 to 0.2, 0.01 to 0.2, 0.011 to 0.2, 0.009 to 0.15, 0.01 to 0.15, 0.011 to 0.15, 0.011 to 0.12, 0.01 to 0.12, or 0.011 to 0.12. As another example, the etching ratio in which the composition (30) etches the first region (21) at a first etching rate and the composition (30) etches the second region (22) at a second etching rate may be 0.05 to 1.0, 0.07 to 1.0, 0.085 to 1.0, 0.05 to 0.5, 0.07 to 0.5, 0.085 to 0.5, 0.05 to 0.2, 0.07 to 0.2, 0.085 to 0.2, 0.05 to 0.15, 0.07 to 0.15, 0.085 to 0.15, 0.05 to 0.12, 0.07 to 0.12, or 0.085 to 0.12.

[0269] FIG. 1b is a schematic diagram illustrating the surface of a metal-containing film (20A) that can be in contact with a composition (30), wherein the etching area ratio, which is the ratio of the first area exposed for contact with the composition (30) in the first region (21) to the second area exposed for contact with the composition (30) in the second region (22), may be 0.05 to 1.0, 0.05 to 0.9, 0.05 to 0.7, 0.05 to 0.5, 0.05 to 0.4, 0.05 to 0.3, or 0.05 to 0.2.

[0270] When the metal-containing film (20A) and the composition (30) come into contact, the high reactivity of the metal contained in the metal-containing film (20A) (e.g., a metal such as molybdenum contained in the second region (22)) is controlled by the interaction of the oxidizing agent, phosphoric acid, organic acid, and etching control agent contained in the composition (30), so that the etching rate of the region containing the metal having relatively high reactivity among the first region (21) and the second region (22) (e.g., the etching rate of the second region (22)) is appropriately controlled, and a part of the first region (21) and a part of the second region (22) are etched, so that a metal-containing film pattern (a pattern of the metal-containing layer, 20) having a substantially flat surface (e.g., substantially no step difference between the first region (21) and the second region (22)) can be formed as shown in FIG. 2, and after the contact step with the composition (30), the metal-containing film pattern (20) Various by-products derived from the metal-containing film (20A) (e.g., metal oxides derived from the metal-containing film (20A), such as molybdenum oxide) may not substantially remain on the surface. For example, whether the by-products remain can be confirmed through TEM (Transmission Electron Microscope) analysis, SEM (Scanning Electron Microscope) analysis, etc.

[0271] Figures 3 and 4 are diagrams briefly illustrating other embodiments of the metal-containing film treatment method.

[0272] Referring to FIG. 3, a substrate (10) is provided with an additional material (40) disposed adjacent to the metal-containing film (20A) in addition to the metal-containing film (20A). For the description of the metal-containing film (20A) and the substrate (10) of FIG. 3, respectively, refer to FIG. 1.

[0273] The additional material (40) of FIG. 3 may be spaced apart from the metal-containing film (20A) or may be in contact with at least some part. In this specification, the additional material (40) refers to a material that is placed adjacent to the metal-containing film (20A) in addition to the metal-containing film (20A) and exists in an area that can be affected by the composition (30) when the metal-containing film (20A) is treated using the composition (30).

[0274] 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 various known materials.

[0275] The insulating material may include various oxides, nitrides, oxynitrides, high dielectric materials, or combinations thereof. For example, the insulating material may include silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, hafnium oxide, hafnium oxynitride, zirconium oxide, or combinations thereof. The hafnium oxide and hafnium oxynitride may optionally further include Si, Ta, Ti, Zr, or any combination thereof. As another example, the insulating material may include TEOS (tetraethyl orthosilicate), HSQ (hydrogen silsesquioxane), MSQ (methyl silsesquioxane), etc.

[0276] The above semiconductor material may include, for example, a material that can be included in a channel, etc., such as a Group IV semiconductor material such as silicon, germanium (Ge), silicon germanium (SiGe), silicon carbide (SiC), etc., a Group III-V semiconductor material such as gallium arsenide (GaAs), indium arsenide (InAs), indium phosphide (InP), an oxide semiconductor, a nitride semiconductor, an oxynitride semiconductor, etc. The above oxide semiconductor may include, for example, IGZO (Indium Gallium Zinc Oxide), ITZO (Indium Tin Zinc Oxide), ITGO (Indium Tin Gallium Oxide), IWO (Indium Tungsten Oxide), ITO (Indium Tin Oxide), ZnO, Cu2O, or any combination thereof.

[0277] As shown in FIG. 3, a metal-containing film (20A) including a first region (21) and a second region (22) and an additional material (40) may be brought into contact with a composition (30) so that a portion of the metal-containing film (20A) may be removed. For example, during the etching, cleaning, and / or polishing process of the metal-containing film (20A) including the first region (21) and the second region (22), the metal-containing film (20A) may be brought into contact with the composition (30). The composition (30) includes an oxidizing agent, phosphoric acid, an organic acid, and an etching regulator as described in the present specification, and a detailed description thereof is to be found in the present specification.

[0278] When the metal-containing film (20A) comes into contact with the composition (30), a portion of the metal-containing film (20A) may be removed. Specifically, when the metal-containing film (20A) and the composition (30) come into contact, the high reactivity of the metal contained in the metal-containing film (20A) (e.g., a metal such as molybdenum contained in the second region (22)) is controlled by the interaction of the oxidizing agent, phosphoric acid, organic acid, and etching control agent contained in the composition (30), thereby appropriately controlling the etching rate of the region containing the metal having relatively high reactivity among the first region (21) and the second region (22) (e.g., the etching rate of the second region (22)), so that a portion of the first region (21) and a portion of the second region (22) are etched, and as shown in FIG. 4, a metal-containing film pattern (20) having a substantially flat surface (e.g., substantially no step difference between the first region (21) and the second region (22)) can be formed, and after the contact step with the composition (30), the above Various by-products derived from the metal-containing film (20A) (e.g., metal oxides derived from the metal-containing film (20A), such as molybdenum oxide) may not substantially remain. In addition, additional materials (40), including at least one of insulating materials and semiconductor materials, may not substantially be damaged by the composition (30).

[0279] Method for manufacturing electronic devices

[0280] High-quality electronic devices can be fabricated using the composition described above. Accordingly, a method for manufacturing electronic devices using the above composition can be provided.

[0281] According to one aspect,

[0282] As a method for manufacturing an electronic device including a transistor,

[0283] The above transistor is,

[0284] channel;

[0285] A source and a drain electrically connected to the above channel and spaced apart from each other; and

[0286] Gate electrode;

[0287] A gate insulating film disposed between the gate electrode and the channel;

[0288] Includes,

[0289] The step of providing the gate electrode is,

[0290] A step of providing a barrier layer comprising a metal nitride, a metal oxide nitride, or a combination thereof;

[0291] A step of providing a conductive layer including a conductive metal; and

[0292] A step of 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 a gate electrode;

[0293] A method for manufacturing an electronic device, including, is provided.

[0294] The above channel may include, for example, semiconductor materials described in this specification. For example, the channel may include Group IV semiconductor materials such as silicon, germanium (Ge), silicon germanium (SiGe), silicon carbide (SiC), etc., Group III-V semiconductor materials such as gallium arsenide (GaAs), indium arsenide (InAs), indium phosphide (InP), etc., oxide semiconductors, nitride semiconductors, oxynitride semiconductors, etc. The oxide semiconductor may include, for example, IGZO (Indium Gallium Zinc Oxide), ITZO (Indium Tin Zinc Oxide), ITGO (Indium Tin Gallium Oxide), IWO (Indium Tungsten Oxide), ITO (Indium Tin Oxide), ZnO, Cu2O, or any combination thereof.

[0295] The gate insulating film may include an insulating material capable of electrically insulating the gate electrode and the channel. For example, the gate insulating film may include various oxides, nitrides, oxynitrides, high dielectric 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. The hafnium oxide and hafnium oxynitride may optionally further include Si, Ta, Ti, Zr, or any combination thereof.

[0296] 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.

[0297] To provide the gate electrode described above, a barrier layer and a conductive layer may be provided. For example, a conductive layer may be provided on the surface of the barrier layer after the barrier layer is formed; however, depending on the structure of the channel and / or gate electrode, various variations are possible, such as forming a barrier layer on the surface of the conductive layer after the conductive layer is formed.

[0298] The barrier layer may be provided to prevent peripheral diffusion of a conductive metal (e.g., metal ions) included in the conductive layer and / or to facilitate the smooth deposition of the conductive layer.

[0299] For a detailed description of each metal nitride and / or metal oxynitride that may be included in the above barrier layer, refer to the description of each metal nitride and / or metal oxynitride that may be included in the first region of the metal-containing film in this specification.

[0300] According to one embodiment, the barrier layer comprises titanium nitride, titanium oxide nitride, or a combination thereof, and each of the titanium nitride and titanium oxide nitride may optionally further comprise indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

[0301] For a detailed description of a conductive metal that may be included in the above conductive layer, refer to the description of a conductive metal that may be included in the second region of the metal-containing film in this specification.

[0302] According to one embodiment, the conductive layer may include tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

[0303] Next, the barrier layer and the conductive layer can be brought into contact with a composition as described in this specification, and a portion of the barrier layer and a portion of the conductive layer can be etched to form a gate electrode.

[0304] When the barrier layer and the conductive layer are in contact with the composition as described in this specification, the high reactivity of the conductive metal contained in the conductive layer is controlled by the interaction of the oxidizing agent, phosphoric acid, organic acid, and etching control agent included in the composition. Consequently, the etching rate of the conductive layer is appropriately controlled, and a portion of the barrier layer and a portion of the conductive layer are etched, thereby forming a gate electrode having a substantially flat surface (e.g., substantially no step difference between the barrier layer and the conductive layer). Furthermore, after the contact step with the composition, various by-products originating from the conductive layer (e.g., oxides of the conductive metal) may not substantially remain on the surface of the gate electrode. In addition, at least one of the channel and the gate insulating film disposed adjacent to the gate electrode may not be substantially damaged by the composition, thereby enabling the fabrication of a high-quality electronic device including a gate electrode having a precise pattern without damage to the region adjacent to the gate electrode.

[0305] The above electronic device may be a semiconductor memory device.

[0306] For example, the electronic device may include non-volatile memory devices such as volatile memory devices, such as dynamic random access memory ("DRAM") or static random access memory ("SRAM") devices, resistive random access memory ("ReRAM") devices, electrically eraseable programmable read-only memory ("EEPROM") devices, flash memory (which may also be considered a subset of EEPROM), ferroelectric random access memory ("FRAM") devices and magnetoresistive random access memory ("MRAM") devices, and other semiconductor devices capable of storing information.

[0307] According to one embodiment, the electronic device may be a DRAM device.

[0308] Hereinafter, with reference to FIGS. 5, 6a, 6b, 7, 8, and 9, the method for manufacturing the electronic device will be described in more detail.

[0309] FIG. 5 is a schematic plan view of an electronic device (3000) according to an exemplary embodiment, and FIG. 6 is a perspective view of the electronic device (3000) shown in FIG. 5. The electronic device (3000) of FIG. 5 may be a DRAM device.

[0310] Referring to FIGS. 5, 6a and 6b, the electronic device (3000) includes a plurality of unit devices (3100) arranged in an array form. Here, each unit device (3100) has a 1T1C structure composed of one transistor and one capacitor.

[0311] The electronic device (3000) includes a transistor structure (100) and a plurality of capacitors (3500) provided in the transistor structure (100). The transistor structure (100) may be a vertical channel array transistor structure including channels arranged vertically with respect to a substrate (see FIG. 6a), a channel array transistor structure including channels arranged horizontally and stacked with respect to a substrate (see FIG. 6b), etc.

[0312] 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) may be provided to extend in a first direction (e.g., x-axis direction), and each bit line (160) may be provided to extend in a second direction (e.g., y-axis direction) that intersects the first direction. Transistors are disposed at points where the plurality of gate electrodes (150) and the plurality of bit lines (160) intersect.

[0313] FIGS. 7 to 9 are drawings briefly illustrating a part of the manufacturing process of the transistor structure (100) shown in FIG. 6a.

[0314] The transistor structure (100) of FIG. 7 includes a substrate (110) and a plurality of channels (140) arranged in an array form on the substrate (110). Here, the plurality of channels (140) may be arranged in a two-dimensional array form on a plane (e.g., an xy plane) of the substrate (110).

[0315] The substrate (110) may include, for example, silicon (Si). As a specific example, the substrate (110) may be a silicon substrate doped with n-type impurities. However, this is merely an example, and in addition, the substrate (110) may include, for example, group IV semiconductor materials such as germanium (Ge), silicon germanium (SiGe), silicon carbide (SiC), group III-V semiconductor materials such as gallium arsenide (GaAs), indium arsenide (InAs), indium phosphide (InP), oxide semiconductors, nitride semiconductors, oxynitride semiconductors, etc.

[0316] Each of the plurality of channels (140) may be provided by extending vertically from the substrate (110). Here, each channel (140) may be provided by protruding vertically from the upper surface of the substrate (110). Each channel (140) may include the same semiconductor material as the semiconductor substrate (110) by being formed integrally with the substrate (110). Although the channel (140) of FIG. 7 is formed integrally with the substrate (110), various variations are possible, such as the channel (140) being formed separately from the substrate (110).

[0317] 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 the drain (D) can be formed through the formation of a doping region. The capacitor (3500) shown in FIG. 5 can be connected to the drain (D) provided at the top of the channel (140).

[0318] Sources (S) are provided on the upper side of the substrate (110) in an array form corresponding to the channels (140). Below these sources (S), a plurality of bit lines (160) are provided extending along a second direction (e.g., the y-axis direction). Here, each bit line (160) can electrically connect the sources (S) arranged along the second direction. The plurality of bit lines (160) may include the same semiconductor material as the substrate (110) by being formed inside the substrate (110). Various variations are possible, such as the bit lines (160) of FIG. 7 being formed separately using a material distinct from the substrate (110).

[0319] A plurality of insulating materials (170) may be provided on a substrate (110) between a plurality of bit lines (160). The plurality of insulating materials (170) may be provided to extend along a second direction parallel to the plurality of bit lines (160) so as to separate the plurality of bit lines (160) within the substrate (110). The insulating material (170) may include, for example, silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, hafnium oxide, hafnium oxynitride, zirconium oxide, or a combination thereof.

[0320] A gate insulating film (130) is provided on the surface of the channels (140). The gate insulating film (130) may comprise an insulating material as described herein, for example, silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, hafnium oxide, hafnium oxynitride, zirconium oxide, or a combination thereof.

[0321] As described above, among the substrate (110) provided with channels (140) and a gate insulating film (130), 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 within a trench defined by the gate insulating film (130), as illustrated in FIG. 7. For example, the conductive layer (152) may be provided on the surface of the barrier layer (151) after the barrier layer (151) is formed, but various variations are possible, such as forming the barrier layer (151) on the surface of the conductive layer (152) after the conductive layer (152) is formed, depending on the structure of the channels (140) and / or the gate electrode (150). For descriptions of the metal nitride and / or metal oxynitride included in the barrier layer (151) and the conductive metal included in the conductive layer (152), respectively, refer to what is described in this specification.

[0322] Next, as shown in FIG. 7, an embedded insulating layer (180) is provided within a trench partially defined by the conductive layer (152). The embedded insulating layer (180) can serve to protect the gate electrode (150) of FIG. 8 from the penetration of oxygen, etc. After forming the embedded insulating layer (180), if necessary, a flattening process may be additionally performed so that the upper surface of the barrier layer (151) and the conductive layer (152) is exposed.

[0323] Next, the upper surface 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) to form a gate electrode (150) having a pattern as shown in FIG. 8. The composition (30) in FIG. 7 includes an oxidizing agent, phosphoric acid, an organic acid, and an etching control agent as described in the present specification, and a detailed description thereof is provided in the present specification.

[0324] The etching rate ratio in which the composition (30) etches the barrier layer (151) by the first etching rate to the composition (30) etches the conductive layer (152) by the second etching rate may be 0.009 or higher. For example, the etching ratio in which the composition (30) etches the barrier layer (151) at a first etching rate and the composition (30) etches the conductive layer (152) at a second etching rate may be 0.009 to 1.0, 0.01 to 1.0, 0.011 to 1.0, 0.009 to 0.5, 0.01 to 0.5, 0.011 to 0.5, 0.009 to 0.2, 0.01 to 0.2, 0.011 to 0.2, 0.009 to 0.15, 0.01 to 0.15, 0.011 to 0.15, 0.009 to 0.12, 0.01 to 0.12, or 0.011 to 0.12. As another example, the etching ratio in which the composition (30) etches the barrier layer (151) at a first etching rate and the composition (30) etches the conductive layer (152) at a second etching rate may be 0.05 to 1.0, 0.07 to 1.0, 0.085 to 1.0, 0.05 to 0.5, 0.07 to 0.5, 0.085 to 0.5, 0.05 to 0.2, 0.07 to 0.2, 0.085 to 0.2, 0.05 to 0.15, 0.07 to 0.15, 0.085 to 0.15, 0.05 to 0.12, 0.07 to 0.12, or 0.085 to 0.12.

[0325] Meanwhile, the etching area ratio, which is the first area exposed for contact with the composition (30) in the barrier layer (151) divided by the second area exposed for contact with the composition (30) in the conductive layer (152), may be 0.05 to 1.0, 0.05 to 0.9, 0.05 to 0.7, 0.05 to 0.5, 0.05 to 0.4, 0.05 to 0.3, or 0.05 to 0.2.

[0326] When the barrier layer (151) and the conductive layer (152) come into contact with the composition (30), the high reactivity of the conductive metal contained in the conductive layer (152) is controlled by the interaction of the oxidizing agent, phosphoric acid, organic acid, and etching control agent contained in the composition (30), so that the etching rate of the conductive layer (152) is appropriately controlled and a part of the barrier layer (151) and a part of the conductive layer (152) are etched, so that a gate electrode (150) having a substantially flat upper surface (e.g., there is substantially no step difference between the barrier layer (151) and the conductive layer (152)) can be formed as shown in FIG. 8, and after the contact step with the composition (30), various by-products (e.g., oxides of the conductive metal) originating from the conductive layer (152) may not substantially remain on the surface of the gate electrode (150). In addition, the channel (140), gate insulating film (130), and buried insulating layer (180) disposed adjacent to the gate electrode (150) may not be substantially damaged by the composition (30), so that a high-quality electronic device (3000) including a gate electrode (150) having a precise pattern can be manufactured without damage to the area adjacent to the gate electrode (150), for example, the channel (140), gate insulating film (130), and buried insulating layer (180).

[0327] In FIG. 8, 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 that intersects the aforementioned second direction. For example, the first direction may be a direction that is orthogonal to the second direction. However, it is not necessarily limited thereto.

[0328] Each gate electrode (150) is provided to correspond to channels (140) arranged along a first direction. Specifically, each gate electrode (150) may be provided to surround channels (140) arranged along a first direction. Such gate electrodes (150) may serve as word lines.

[0329] A plurality of gate electrodes (150) may be provided to intersect with a plurality of insulating materials (170) provided on their lower portions. The upper surface of the insulating materials (170) may be provided to be adjacent to the lower surface of the gate electrodes (150). Here, the upper portion of the insulating materials (170) may be provided to protrude from the bottom of the gate electrodes (150), but is not limited thereto.

[0330] Next, as illustrated in FIG. 9, 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 serve to further insulate the gate electrode (150) and the channel (140), and may include, for example, an insulating material as described in the present specification.

[0331] Method for manufacturing electronic devices

[0332] Referring to FIG. 10, one embodiment of a method for manufacturing an electronic device may include the step of preparing a substrate provided with a metal-containing film (S100); the step of contacting the metal-containing film with a composition as described herein (S110); and the step of fabricating an electronic device using a subsequent process (120). The subsequent process may include various known processes for fabricating electronic devices, such as, for example, a capacitor formation process.

[0334] Example 1 and Comparative Examples C1 to C4

[0335] The compositions of Example 1 and Comparative Examples C1 to C4 were prepared by mixing substances weighed according to the amounts listed in Table 1 as an oxidizing agent, an inorganic acid, an organic acid, and an etching control agent, respectively. The remainder of each composition is water (deionized water). The numbers in parentheses in Table 1 represent the weight of the corresponding substance per 100 wt% of the composition, and the unit is wt%.

[0337] Evaluation Example 1

[0338] The composition of Example 1 was placed in each of three beakers and heated to 60°C. Then, 1 cm x 1 cm specimens of a titanium nitride-containing film, a molybdenum film, and a silicon oxide film were immersed in each beaker for 1 minute. Subsequently, the thicknesses of the titanium nitride-containing film, the molybdenum film, and the silicon oxide film, respectively, were measured using an ellipsometer (M-2000, JAWoolam), a 4-point resistance meter, and XRF (X-Ray Fluorescence Spectroscopy). The etching rate of the composition of Example 1 on the titanium nitride-containing film (also referred to as the "titanium nitride-containing film etching rate"), the etching rate of the composition of Example 1 on the molybdenum film (also referred to as the "molybdenum film etching rate"), the etching rate ratio R obtained by dividing the titanium nitride-containing film etching rate by the molybdenum film etching rate, and the etching rate of the composition of Example 1 on the silicon oxide film ("silicon oxide film etching rate") Each of the etching rates (also referred to as "rate") was evaluated, and the results were summarized in Table 1 along with the pH of Example 1. The unit of each etching rate is "Å / min". In addition, the presence of molybdenum oxide residue was evaluated by analyzing the surface of the molybdenum film obtained after immersion in the composition of Example 1 using TEM (Transmission Electron Microscope) and TEM-EDS (Energy-dispersive X-ray spectroscopy), and the results were summarized in Table 1.

[0339] The above tests were repeated using each of the compositions of Comparative Examples C1 to C4, and the results are summarized in Table 1. The molybdenum films immersed in Comparative Examples C3 and C4 were all dissolved, so it was impossible to evaluate the etching rate of the molybdenum films in Comparative Examples C3 and C4 and the R value using them. A photograph of the molybdenum film surface obtained after immersion in the composition of Example 1 is shown in Fig. 11a, and a photograph of the molybdenum film surface obtained after immersion in the composition of Comparative Example C1 is shown in Fig. 11b.

[0340] Oxidizing agent Inorganic acid organic acids Etching regulator pH Titanium nitride-containing film etching rate (Å / min) Molybdenum film etching rate (Å / min) R Silicon oxide film etching rate (Å / min) Whether molybdenum oxide is observed Example 1 H2O2(0.5) Iodine (0.02) Phosphoric acid (60) Acetic acid (10) A29(1) -0.4 2.5 190 0.013 <1 X Comparative Example C1 H2O2(0.5) - Phosphoric acid (60) Acetic acid (10) A29(1) -0.3 2.1 185 0.011 <1 O Comparative Example C2 - Iodine (0.02) Phosphoric acid (60) Acetic acid (10) A32(1) -0.4 0.5 64 0.008 <1 X Comparative Example C3 - Iodine (1) Phosphoric acid (60) Acetic acid (10) A31(1) -0.4 1.8 N / A N / A <1 X Comparative Example C4 H2O2(0.5) Iodine (0.02) Phosphoric acid (5) Acetic acid (10) A29(1) 2.5 0.4 N / A N / A <1 X

[0341] X: No molybdenum oxide observed

[0342] O : Molybdenum oxide observed

[0343]

[0345] From Table 1, Fig. 11a and Fig. 11b,

[0346] i) The composition of Comparative Example C1 can produce byproducts such as molybdenum oxide after contact with a molybdenum film, and

[0347] ii) In the composition of Comparative Example C2, the etching rate of the molybdenum film is greater than the etching rate of the titanium nitride-containing film, so not only is over-etching of the molybdenum film expected when the titanium nitride-containing film and the molybdenum film are etched simultaneously, but the etching rates of the titanium nitride-containing film and the molybdenum film are lower than the etching rates of the titanium nitride-containing film and the molybdenum film, respectively, of Example 1, so the etching process efficiency may be poor when using the composition of Comparative Example C2, and

[0348] iii) In Comparative Examples C3 and C4, the etching rate of the molybdenum film is excessively high compared to the etching rate of the titanium nitride-containing film to the extent that it dissolves all of the immersed molybdenum film, so over-etching of the molybdenum film is expected when the titanium nitride-containing film and the molybdenum film are etched simultaneously, but

[0349] iv) It can be confirmed that the composition of Example 1 allows the etching rate of the molybdenum film relative to the etching rate of the titanium nitride-containing film to be appropriately controlled without damage to the adjacent silicon oxide film or the generation of byproducts such as molybdenum oxide, thereby substantially preventing over-etching of the molybdenum film when the titanium nitride-containing film and the molybdenum film are etched simultaneously.

[0351] Examples 11 to 13

[0352] The compositions of Examples 11 to 13 were prepared by mixing substances weighed according to the amounts listed in Table 2 as an oxidizing agent, an inorganic acid, an organic acid, and an etching control agent. The remainder of each composition is water (deionized water). The numbers in parentheses in Table 2 represent the weight of the corresponding substance per 100 wt% of the composition, and the unit is wt%. The weight-average molecular weight of polymer P1 used as the etching control agent in Example 13 is 1600 g / mol, and the content of polymer P1 in Table 5 indicates the content of the solids of polymer P1.

[0354] Evaluation Example 2

[0355] For the compositions of Examples 11 to 13, pH, titanium nitride-containing film etching rate, molybdenum film etching rate, etching rate ratio R (titanium nitride-containing film etching rate divided by molybdenum film etching rate), silicon oxide film etching rate, and the presence of molybdenum oxide residue were evaluated using the same method as described in Evaluation Example 1, and the results are summarized in Table 2. A photograph of the molybdenum film surface obtained after immersion in the composition of Example 11 is shown in FIG. 12.

[0356] Oxidizing agent Inorganic acid organic acids Etching regulator pH Titanium nitride-containing film etching rate (Å / min) Molybdenum film etching rate (Å / min) R Silicon oxide film etching rate (Å / min) Whether molybdenum oxide is observed Example 11 H2O2(0.5) Iodine (0.02) Phosphoric acid (60) Acetic acid (10) A1(1) -0.4 1.8 15.3 0.12 < 1 X Example 12 H2O2(0.5) Iodine (0.02) Phosphoric acid (60) Acetic acid (10) A2(1) -0.4 2.0 18.7 0.11 < 1 X Example 13 H2O2(0.5) Iodine (0.02) Phosphoric acid (60) Acetic acid (10) P1(1) -0.4 1.1 13.0 0.085 < 1 X

[0358]

[0359]

[0361] From Table 2 and Figure 11, it can be seen that the compositions of Examples 11, 12, and 13 allow the etching rate of the molybdenum film relative to the etching rate of the titanium nitride-containing film to be appropriately controlled without damage to the adjacent silicon oxide film or the generation of byproducts such as molybdenum oxide, thereby substantially preventing over-etching of the molybdenum film during simultaneous etching of the titanium nitride-containing film and the molybdenum film. Explanation of the symbols

[0362] 10.. Circuit board 20A.. Metal-containing film 21.. First area 22.. Second area 20.. Metal-containing film pattern 30.. Composition 40.. Additional material 100.. Transistor structure 110.. Circuit board 130.. Gate insulating film 140.. Channel 151.. Barrier layer 152.. Challenge Floor 150.. Gate electrode 160.. Bit line 170.. Insulating material 3000.. Electronic components 3100.. unit element 3500.. capacitor S.. Source D.. Drain

Claims

Claim 1 A method for treating a metal-containing film comprising: a step of preparing a substrate provided with a metal-containing film including a first region and a second region; and a step of contacting the metal-containing film with a composition; wherein the first region and the second region independently comprise 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, wherein the material included in the first region and the material included in the second region are different from each other, and the composition comprises an oxidizing agent, phosphoric acid, an organic acid, and an etching controller, wherein the oxidizing agent comprises hydrogen peroxide and an iodine-containing compound, and the etching controller comprises a nitrogen-containing compound, and has a pH of less than 1. Claim 2 A method for treating a metal-containing film according to claim 1, wherein the first region comprises titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), or any combination thereof, and the second region comprises tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof. Claim 3 A method for treating a metal-containing film according to claim 1, wherein the first region comprises a metal nitride, a metal oxide nitride, or a combination thereof, and the second region comprises a conductive metal. Claim 4 A method for treating a metal-containing film according to claim 1, wherein the first region comprises titanium nitride, titanium oxide nitride, or a combination thereof, and each of the titanium nitride and titanium oxide nitride optionally further comprises indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof. Claim 5 A metal-containing film treatment method according to claim 1, wherein the etching area ratio, in which the first area exposed for contact with the composition in the first region is divided by the second area exposed for contact with the composition in the second region, is 0.05 to 1.

0. Claim 6 A metal-containing film treatment method according to claim 1, wherein the weight ratio of the iodine-containing compound to the hydrogen peroxide in the composition is 1:10 to 1:

100. Claim 7 A metal-containing film treatment method according to claim 1, wherein the content of phosphoric acid in the composition is 10 wt% to 85 wt% per 100 wt% of the composition. Claim 8 A method for treating a metal-containing film according to claim 1, wherein the nitrogen-containing compound in the composition comprises an amine-containing alcohol, an amine-containing acid, a polyalkylene polyamine, a cyclic group-containing amine, a polymer having a nitrogen-containing repeating unit, or a combination thereof. Claim 9 A method for treating a metal-containing film according to claim 1, wherein the composition has a pH of -3.0 to 0.

9. Claim 10 A method for manufacturing an electronic device including a transistor, wherein the transistor comprises: a channel; a source and a drain electrically connected to the channel and spaced apart from each other; and a gate electrode; and a gate insulating film disposed between the gate electrode and the channel; and the step of providing the gate electrode comprises: providing a barrier layer comprising a metal nitride, a metal oxynitride, or a combination thereof; providing a conductive layer comprising a conductive metal; and contacting the barrier layer and the conductive layer with a composition to etch a portion of the barrier layer and a portion of the conductive layer to form a gate electrode; wherein the composition comprises an oxidizing agent, a phosphoric acid, an organic acid, and an etching controller, wherein the oxidizing agent comprises hydrogen peroxide and an iodine-containing compound, and the etching controller comprises a nitrogen-containing compound, and has a pH of less than 1. Claim 11 A method for manufacturing an electronic device according to claim 10, wherein the barrier layer comprises titanium nitride, titanium oxide nitride, or a combination thereof, and each of the titanium nitride and titanium oxide nitride optionally further comprises 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. Claim 12 A method for manufacturing an electronic device according to claim 10, further comprising the step of contacting the barrier layer and the conductive layer with the composition to form a gate electrode by etching a portion of the barrier layer and a portion of the conductive layer, and then providing an insulating layer on the surface of the etched barrier layer and the surface of the etched conductive layer. Claim 13 A composition comprising an oxidizing agent, phosphoric acid, an organic acid, and an etching controller, wherein the oxidizing agent comprises hydrogen peroxide and an iodine-containing compound, the etching controller comprises a nitrogen-containing compound, and has a pH of less than 1. Claim 14 A composition according to claim 13, wherein the content of the oxidizing agent is 0.001 wt% to 10 wt% per 100 wt% of the composition. Claim 15 A composition according to claim 13, wherein the weight ratio of the iodine-containing compound to the hydrogen peroxide is 1:10 to 1:

100. Claim 16 A composition according to claim 13, wherein the content of the phosphoric acid is 10 wt% to 85 wt% per 100 wt% of the composition. Claim 17 A composition according to claim 13, wherein the organic acid comprises a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, or any combination thereof. Claim 18 A composition according to claim 13, wherein the nitrogen-containing compound comprises an amine-containing alcohol, an amine-containing acid, a polyalkylene polyamine, a cyclic group-containing amine, a polymer having a nitrogen-containing repeating unit, or a combination thereof. Claim 19 A composition according to claim 13, wherein the content of the etching regulator is 0.01 wt% to 5 wt% per 100 wt% of the composition. Claim 20 A composition according to claim 13, having a pH of -3.0 to 0.9.

Images