Composition, method for treating metal-containing film, and method for manufacturing electronic elements

Abstract

The present invention provides a composition, a method for processing a metal-containing film, and a method for manufacturing an electronic device. [Solution] A composition is provided comprising an oxidizing agent, phosphoric acid, an organic acid, and an etching modifier, wherein the oxidizing agent comprises hydrogen peroxide, an iodine-containing compound, or a combination thereof, and the etching modifier comprises a hydroxyl-free and nitrogen-containing compound, and the composition has a pH of 2.0 or less. A method for treating a metal-containing film using the same and a method for manufacturing an electronic device using the same are also provided.

Description

[Technical Field]

[0001] The present 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 consumer demands for superior performance and low cost, there is a need for increased integration density and improved reliability of various electronic components, such as semiconductor devices. As semiconductor device integration density increases, damage to the components during the manufacturing process has a greater impact on the reliability and electrical characteristics of the semiconductor device. In particular, various processing steps, such as etching, cleaning, and polishing, can be performed on a given film (e.g., a metal-containing film) during the semiconductor device manufacturing process. Therefore, there is a persistent need for compositions with appropriate etching rates and other properties to effectively perform these metal-containing film processing steps. [Overview of the project] [Problems that the invention aims to solve]

[0003] The problem that this invention aims to solve is to provide a composition that enables effective etching rate control for 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 for solving the problem]

[0004] According to one aspect, It contains an oxidizing agent, phosphoric acid, organic acid, and an etching controller. The oxidizing agent includes hydrogen peroxide, an iodine-containing compound, or a combination thereof. The etching modifier comprises a hydroxyl-free and nitrogen-containing compound. The nitrogen-containing compound without a hydroxy group includes a compound represented by the following chemical formula 5, a compound represented by the following chemical formula 6, or a combination thereof, A composition having a pH of 2.0 or less is provided: <Chemical formula 5> T 52 -[(L5) a5 -T 51 <Chemical formula 6> CY6-[L6-N(R 61 )(R 62 )] a6 In the chemical formula 5, L5 is *-C(Z 51 )(Z 52 )-*’, *-N(Z 53 )-*’ or *-C(=O)-*’, In the chemical formula 5, a5 is an integer of 2 to 30, In the chemical formula 5, T 51 is *-N(R 51 )(R 52 ) and T 52 is *-N(R 53 )(R 54 ), In the chemical formula 6, the ring CY6 is a saturated or unsaturated carbocyclic group having 5 to 15 carbon atoms, a saturated heterocyclic group having 2 to 15 carbon atoms, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a carbazole group, a dibenzofuran group or a dibenzothiophene group, In the chemical formula 6, L6 is a single bond or a C1-C 30 alkylene group, In the chemical formula 6, a6 is an integer of 1 to 5, In the chemical formulas 5 and 6, Z 51 , Z 52 , Z 53 , R 51 , R 52 , R 53 , R 54 , R 61 and R 62 are independent of each other, hydrogen or an amino group; or an amino group, mono(C1-C 30Alkyl)amino group, di(C1-C 30 Alkyl)amino group, *-C(=O)-N(Q 51 )(Q 52 ), or any combination thereof, C1-C 30 Alkyl alkyl group; Q 51 and Q 52 They are independent of each other, hydrogen; or Amino group, mono(C1-C) 30 Alkyl)amino group, di(C1-C 30 C1-C amino groups, or combinations thereof, substituted or unsubstituted. 30 Alkyl alkyl group; * and *' are bonding sites with adjacent atoms, respectively.

[0005] According to other embodiments, A step of preparing a substrate provided with a metal-containing film including a first region and a second region; and The step of bringing the metal-containing film into contact with the composition; The first and second regions independently contain 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. A method for processing a metal-containing film is provided, wherein the substance contained in the first region and the substance contained in the second region are different from each other.

[0006] In another embodiment, a method for manufacturing an electronic element including a transistor, The aforementioned transistor is Channels and The channel is electrically connected to a source and a drain, which are arranged at a distance from each other. Terminal gate and, The gate insulating film is disposed between the gate electrode and the channel, The method for manufacturing the electrical element includes the steps of providing a barrier layer comprising a metal nitride, a metal oxynitride, or a combination thereof, The steps include providing a conductive layer containing a conductive metal, A method for manufacturing an electronic element is provided, which includes the steps of bringing the barrier layer and the conductive layer into contact with a composition, and etching a part of the barrier layer and a part of the conductive layer to form the gate electrode. [Effects of the Invention]

[0007] The composition allows for easy control of the etching rate for various metal-containing films and can be effectively used in various processing steps for the metal-containing films, such as etching, cleaning, and polishing. By processing metal-containing films using the composition, high-quality electronic devices and / or electronic apparatus can be manufactured. [Brief explanation of the drawing]

[0008] [Figure 1A] This is a simplified diagram illustrating one example of a method for processing metal-containing films. [Figure 1B] This is a simplified diagram showing the surface of the metal-containing film 20a in Figure 1A that may come into contact with composition 30. [Figure 2] This is a simplified diagram illustrating one example of a method for processing metal-containing films. [Figure 3] This diagram briefly illustrates another example of a method for processing metal-containing films. [Figure 4] This diagram briefly illustrates another example of a method for processing metal-containing films. [Figure 5] This is a schematic plan view of an electronic component based on an illustrative example. [Figure 6A] Figure 5 is a perspective view showing an example of an electronic element illustrated in the diagram. [Figure 6B] Figure 5 is a perspective view showing another embodiment of the electronic device illustrated. [Figure 7] Figure 6A is a simplified diagram illustrating part of the manufacturing process of the transistor structure shown. [Figure 8] Figure 6A is a simplified diagram illustrating part of the manufacturing process of the transistor structure shown. [Figure 9] Figure 6A is a simplified diagram illustrating part of the manufacturing process of the transistor structure shown. [Figure 10] This flowchart shows an example of an electronic device manufacturing method. [Figure 11A] This is the 1H NMR data of compound A1 after mixing with high-concentration (70 wt%) phosphoric acid and heating at a high temperature (60°C). [Figure 11B] This is the 1H NMR data of PEI (polyethyleneimine) after mixing with high-concentration (70 wt%) phosphoric acid and heating at a high temperature (60°C). [Figure 12] This is a TEM (Transmission Electron Microscope) image of Sample 1, in which a molybdenum film and a titanium nitride-containing film are placed between two silicon oxide films. [Figure 13A] This is a TEM image of Sample 1 immersed in the composition of Example 1. [Figure 13B] This is a TEM image of Sample 1 immersed in the composition of Comparative Example C2. [Modes for carrying out the invention]

[0009] metal-containing film The metal-containing film may contain 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.), lanthanide metals (e.g., lanthanum (La), europium (Eu), terbium (Tb), ytterbium (Yb), etc.), transition metals (e.g., scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), etc.), and other metals. These may include phnium (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., transition metals (e.g., aluminum (Al), gallium (Ga), indium (In), thallium (Tl), tin (Sn), bismuth (Bi), etc.), or any combination thereof.

[0010] According to one example, 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.

[0011] Furthermore, according to other examples, the metal-containing film may contain two or more different metals.

[0012] Furthermore, according to other examples, the metal-containing film may contain titanium.

[0013] Furthermore, according to other embodiments, the metal-containing film may, i) contain titanium (Ti), and ii) optionally further contain, 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.

[0014] The metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.

[0015] According to one embodiment, the metal-containing film comprises a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof, wherein each of the metal, the metal of the metal nitride, the metal of the metal oxide, and the metal of the metal oxynitride 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.

[0016] According to other examples, the metal-containing film may include metal nitrides, metal oxynitrides, or combinations thereof (for example, titanium nitrides, titan oxynitrides, or combinations thereof).

[0017] Furthermore, according to other examples, the metal-containing film may contain the aforementioned metals (for example, conductive metals such as tungsten, molybdenum, and ruthenium).

[0018] Furthermore, according to other embodiments, the metal-containing film may include i) metal nitrides, metal oxynitrides, or combinations thereof as described above (e.g., titanium nitride, titan oxynitride, or combinations thereof), and ii) conductive metals (e.g., conductive metals such as tungsten, molybdenum, and ruthenium).

[0019] In further embodiments, the metal-containing film comprises titanium nitride, titan oxynitride, or a combination thereof, and may further comprise tungsten, molybdenum, ruthenium, or any combination thereof, in addition to titanium nitride, titan oxynitride, or a combination thereof. Each of the titanium nitride and titan oxynitride may optionally further comprise indium, aluminum, lanthanum, scandium, gallium, silicon, or any combination thereof.

[0020] Furthermore, according to other embodiments, the metal-containing film 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), and the like.

[0021] The metal-containing film may be a single-layer structure containing one or more substances, or a multilayer structure containing different substances. The multiple films contained in the multilayer structure may be stacked vertically or arranged horizontally on the substrate. The single-layer and multilayer structures may have various three-dimensional patterns (e.g., via holes, trenches, etc.).

[0022] According to one embodiment, the metal-containing film comprises a first region and a second region, the first region and the second region independently comprising 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 substances contained in the first region and the substances contained in the second region may be different from each other.

[0023] According to other embodiments, the first region may contain titanium.

[0024] Furthermore, according to other embodiments, the first region may further optionally include, i) titanium (Ti), and ii) 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.

[0025] Furthermore, according to other embodiments, the second region may include tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

[0026] Furthermore, according to other embodiments, 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.

[0027] In further embodiments, the first region may include a metal nitride, a metal oxynitride, or a combination thereof, and the second region may include a conductive metal.

[0028] 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.

[0029] In further embodiments, the first region comprises titanium nitrides, titan oxynitrides, or combinations thereof, each of which may optionally further include indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

[0030] Furthermore, according to other embodiments, 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), and the like.

[0031] In this specification, etching of any film means that some or more of the material constituting the film is removed.

[0032] composition The composition may include an oxidizing agent, phosphoric acid, an organic acid, and an etching controller.

[0033] The above composition can be used in a variety of processing steps for metal-containing films as described herein, such as etching, cleaning, and polishing steps.

[0034] The composition may further contain a polar solvent (for example, water).

[0035] According to one example, the composition does not contain a fluorine-containing compound. Although not intended to be limited by any particular theory, if the composition contains a fluorine-containing compound, when the metal-containing film is treated with it, adjacent materials located adjacent to the metal-containing film, such as various oxides, may be damaged, as described later, potentially leading to a decrease in the performance of electronic and / or semiconductor devices.

[0036] In one embodiment, the composition may consist of an oxidizing agent, phosphoric acid, an organic acid, an etching modifier, and a polar solvent (e.g., water). In another embodiment, the composition may consist substantially of an oxidizing agent, phosphoric acid, an organic acid, an etching modifier, and a polar solvent (e.g., water). In yet another embodiment, the composition may contain an oxidizing agent, phosphoric acid, an organic acid, an etching modifier, with the remainder being water.

[0037] Oxidizing agent The oxidizing agent plays a role in etching a portion or more of the metal-containing film and may include hydrogen peroxide, an iodine-containing compound, or a combination thereof.

[0038] According to one example, the oxidizing agent may include hydrogen peroxide, periodic acid (H5IO6 and / or HIO4), iodic acid (HIO3), or any combination thereof.

[0039] According to other examples, the oxidizing agent may include at least one of hydrogen peroxide and periodic acid.

[0040] Furthermore, according to other examples, the oxidizing agent may include hydrogen peroxide.

[0041] Furthermore, according to other examples, the oxidizing agent may include periodic acid.

[0042] Furthermore, according to other examples, the oxidizing agent is also hydrogen peroxide.

[0043] Furthermore, according to other examples, the oxidizing agent is also periodic acid.

[0044] Furthermore, according to other embodiments, the composition does not contain a fluorine-containing compound (e.g., HF, NH4F, etc.) as an oxidizing agent. Although not intended to be limited by any particular theory, if the composition contains a fluorine-containing compound as an oxidizing agent, when the metal-containing film is treated with it, adjacent materials located adjacent to the metal-containing film, such as various oxides, may be damaged, leading to a decrease in the performance of electronic and / or semiconductor devices.

[0045] The content (by weight) of the oxidizing agent is, for example, 0.001wt% to 3wt%, 0.001wt% to 1wt%, 0.001wt% to 0.7wt%, 0.001wt% to 0.5wt%, 0.005wt% to 3wt%, 0.005wt% to 1wt%, and 0.005wt% to 0.7wt% per 100wt% of the composition. It is also 0.005wt%~0.5wt%, 0.01wt%~3wt%, 0.01wt%~1wt%, 0.01wt%~0.7wt%, 0.01wt%~0.5wt%, 0.02wt%~3wt%, 0.02wt%~1wt%, 0.02wt%~0.7wt%, or 0.02wt%~0.5wt%.

[0046] According to one example, the oxidizing agent contains hydrogen peroxide, and the content (weight) of the hydrogen peroxide is, for example, 0.001wt% to 3wt%, 0.001wt% to 1wt%, 0.001wt% to 0.7wt%, 0.001wt% to 0.5wt%, 0.01wt% to 3wt%, 0.01wt% to 1wt%, 0.01wt% to 0.7wt%, 0.01wt% to 0.5wt%, and 0.02 wt% per 100 wt% of the composition. wt%~3wt%, 0.02wt%~1wt%, 0.02wt%~0.7wt%, 0.02wt%~0.5wt%, 0.1wt%~3wt%, 0.1wt%~1wt%, 0.1wt%~0.7wt%, 0.1wt%~0.5wt%, 0.3wt%~3wt%, 0.3wt%~1wt%, 0.3wt%~0.7wt%, 0.3wt%~0.5wt%, or also 0.5wt%~0.7wt%.

[0047] According to other examples, the oxidizing agent contains periodic acid, and the content (weight) of the periodic acid is, for example, 0.001wt%~3wt%, 0.001wt%~1wt%, 0.001wt%~0.5wt%, 0.001wt%~0.1wt%, 0.001wt%~0.05wt%, 0.001wt%~0.02wt%, 0.005wt%~3wt%, 0.005wt%~1wt%, 0.005wt%~0.5wt%, 0.005wt%~0.1wt%, and 0.0 It is also 0.05wt%~0.05wt%, 0.005wt%~0.02wt%, 0.01wt%~3wt%, 0.01wt%~1wt%, 0.01wt%~0.5wt%, 0.01wt%~0.1wt%, 0.01wt%~0.05wt%, 0.01wt%~0.02wt%, 0.02wt%~3wt%, 0.02wt%~1wt%, 0.02wt%~0.5wt%, 0.02wt%~0.1wt%, 0.02wt%~0.05wt%, or 0.02wt%~0.03wt%.

[0048] phosphoric acid The phosphoric acid, together with the oxidizing agent, plays a role in etching a portion or more of the metal-containing film.

[0049] According to one example, the composition does not contain sulfuric acid, hydrochloric acid, or nitric acid. While not intended to be limited by any particular theory, the use of sulfuric acid, hydrochloric acid, or nitric acid together with the aforementioned oxidizing agents reduces the stability of the composition, making it unsuitable for use in the processing steps of metal-containing films.

[0050] The phosphoric acid content (by weight) is, for example, 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%, and 50 wt% per 100 wt% of the composition. ~85wt%, 55wt%~85wt%, 10wt%~80wt%, 15wt%~80wt%, 20wt%~80wt%, 25wt%~80wt% , 30wt%~80wt%, 35wt%~80wt%, 40wt%~80wt%, 45wt%~80wt%, 50wt%~80wt%, 55wt%~ 80wt%, 10wt%~75wt%, 15wt%~75wt%, 20wt%~75wt%, 25wt%~75wt%, 30wt%~75wt%, 35wt%~75wt%, 40wt%~75wt%, 45wt%~75wt%, 50wt%~75wt%, 55wt%~75wt%, 10wt%~7 It can also be 0 wt%, 15 wt% to 70 wt%, 20 wt% to 70 wt%, 25 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%, or 60 wt% to 70 wt%.

[0051] organic acid The aforementioned organic acid plays a role in controlling the etching rate of a portion or more of the metal-containing film.

[0052] The aforementioned organic acid may include a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, or any combination thereof.

[0053] The number of carbon atoms in the monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid, respectively, can be 1 to 31, 1 to 20, 1 to 10, 1 to 5, or 2 to 3.

[0054] According to one example, the organic acid is, HCOOH; Aliphatic compounds having 1 to 30 carbon atoms (e.g., 1 to 20 or 1 to 15 carbon atoms) or aromatic compounds having 6 to 30 carbon atoms (e.g., 6 to 15 or 6 to 10 carbon atoms); or any combination thereof; including, At least one hydrogen atom among the aliphatic compound and the aromatic compound is optionally a hydroxyl group, a thiol group, an amino group, or a C1-C group. 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), mono(C1-C 10 Alkyl)amino group (e.g., mono(C1-C5 alkyl)amino group), di(C1-C 10 The alkyl)amino group (e.g., a di(C1-C5 alkyl)amino group), a phenyl group, or any combination thereof may be used as an additional substitute.

[0055] In one example, the aliphatic compound may be a saturated aliphatic compound (e.g., an alkane, a cycloalkane, etc.) or an unsaturated aliphatic compound (e.g., an alkene, an alkyne, a cycloalkene, etc.).

[0056] In other examples, the aliphatic compound may also be an acyclic aliphatic compound (e.g., alkanes, alkenes, alkynes, etc.) or a cyclic aliphatic compound (e.g., cycloalkanes, cycloalkenes, adamantanes, norbornanes, etc.).

[0057] Furthermore, according to other examples, the aliphatic compound may be a linear aliphatic compound (e.g., CH3-CH2-CH2-CH2-CH3, etc.) or a branched aliphatic compound (e.g., CH3-CH(CH3)-CH2-CH3, CH3-C(CH3)2-CH3, etc.).

[0058] Furthermore, according to other examples, the aromatic compound is also benzene.

[0059] Furthermore, according to other examples, the aforementioned organic acids 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, and salicylic acid. This may include acids, or any combination thereof.

[0060] The content of the organic acid is also 0.1wt% to 15wt%, 0.5wt% to 15wt%, 1wt% to 15wt%, 3wt% to 15wt%, 5wt% to 15wt%, 7wt% to 15wt%, 0.1wt% to 13wt%, 0.5wt% to 13wt%, 1wt% to 13wt%, 3wt% to 13wt%, 5wt% to 13wt%, 7wt% to 13wt%, 7wt% to 10wt%, or 10wt% to 13wt% per 100wt% of the composition.

[0061] Etching modifier The etching modifier, together with the organic acid, interacts with various metal atoms in the metal-containing film that is being treated, thereby playing a role in regulating the etching rate and other parameters.

[0062] The etching modifier includes a hydroxyl-free and nitrogen-containing compound. The "hydroxyl-free and nitrogen-containing compound" means a compound that does not contain a hydroxyl group and contains at least one nitrogen atom as a molecular constituent atom.

[0063] Although we do not intend to limit ourselves to a specific theory, when hydroxyl group-containing nitrogen-containing compounds (e.g., alkanolamines) are used together with the aforementioned oxidizing agents, the high hydrophilicity of the hydroxyl groups contained in the hydroxyl group-containing nitrogen-containing compounds prevents smooth interaction with various metal atoms in the metal-containing film, resulting in ineffective etching rate control.

[0064] According to one example, the hydroxyl group-free nitrogen-containing compound may include: i) a compound represented by chemical formula 5 belonging to polyalkylene polyamines; ii) a compound represented by chemical formula 6 belonging to cyclic group-containing amines; or iii) a combination thereof (i.e., a compound represented by chemical formula 5 and a compound represented by chemical formula 6): <Chemical formula 5> T 52 -[(L5) a5 ]-T 51 <Chemical formula 6> CY6-[L6-N(R 61 )(R 62 )] a6 In the aforementioned chemical formula 5, L5 is *-C(Z 51 )(Z 52 )-*', *-N(Z 53 )-*' or *-C(=O)-*', In the aforementioned chemical formula 5, a5 is an integer between 2 and 30. In the chemical formula 5, T51 is, *-N(R 51 )(R 52 ) and T 52 is, *-N(R 53 )(R 54 ) and In the above chemical formula 6, the ring CY6 is a saturated or unsaturated carbon ring group having 5 to 15 carbon atoms, a saturated heterocyclic group having 2 to 15 carbon atoms, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a carbazole group, a dibenzofuran group, or a dibenzothiophene group. In the aforementioned chemical formula 6, L6 is a single bond or C1-C 30 It is an alkylene group, In the aforementioned chemical formula 6, a6 is an integer from 1 to 5. In the aforementioned chemical formulas 5 and 6, Z 51 , Z 52 , Z 53 , R 51 , R 52 , R 53 , R 54 , R 61 and R 62 They are independent of each other, Hydrogen or amino group (*-NH2); or Amino group, mono(C1-C) 30 Alkyl)amino group, di(C1-C 30 Alkyl)amino group, *-C(=O)-N(Q 51 )(Q 52 ), or any combination thereof, C1-C 30 Alkyl alkyl group; Q 51 and Q 52 They are independent of each other, hydrogen; or Amino group, mono(C1-C) 30 Alkyl)amino group, di(C1-C 30 C1-C amino groups, or combinations thereof, substituted or unsubstituted. 30 Alkyl alkyl group; * and *' are bonding sites with adjacent atoms, respectively.

[0065] Furthermore, according to other concrete examples, each L5 in the aforementioned chemical formula 5 is *-C(Z 51 )(Z 52 It is also )-*'.

[0066] Furthermore, according to other concrete examples, each L5 in the aforementioned chemical formula 5 is *-C(Z 51 )(Z 52 )-*' or *-N(Z 53 It is also )-*'.

[0067] Furthermore, according to other concrete examples, in the aforementioned chemical formula 5, a5 is also an integer between 2 and 25, an integer between 2 and 20, an integer between 2 and 15, or an integer between 2 and 11.

[0068] Furthermore, according to other concrete examples, in the aforementioned chemical formula 5, each L5 is *-C(Z 51 )(Z 52 )-*', and a5 is also an integer between 2 and 11.

[0069] Furthermore, according to other concrete examples, each L5 is *-C(Z 51 )(Z 52 )-*' or *-N(Z 53 )-*', and a5 is also an integer between 5 and 11.

[0070] Furthermore, according to other concrete examples, each L5 is *-C(Z 51 )(Z 52 )-*' or *-N(Z 53 )-*' and *-N(Z 53 The number of )-*' can be 1, 2, 3, or 4.

[0071] Furthermore, according to other embodiments, in the aforementioned chemical formula 6, the ring CY6 is a saturated or unsaturated carbon ring group of 5 to 10, or a saturated heterocyclic group of 2 to 10.

[0072] According to still other embodiments, in Chemical Formula 6, ring CY6 is 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 4H-pyran-4-one group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a carbazole group, a dibenzofuran group or a dibenzothiophene group.

[0073] According to still other embodiments, in Chemical Formula 6, L6 is a single bond or a C1-C 10 alkylene group (for example, a C1-C5 alkylene group).

[0074] According to still other embodiments, in Chemical Formula 6, a6 is 1, 2 or 3.

[0075] According to still other embodiments, in Chemical Formula 6, a6 is 1 or 2.

[0076] According to still other embodiments, in Chemical Formulas 5 and 6, Z 51 、Z 52 、Z 53 、R 51 、R 52 、R 53 、R 54 、R 61 and R 62 are independent of each other and are hydrogen or an amino group; or an amino group, a mono(C1-C 10 alkyl)amino group, a di(C1-C 10Alkyl)amino group, *-C(=O)-N(Q 51 )(Q 52 ), or any combination thereof, C1-C 10 Alkyl alkyl group; Q 51 and Q 52 They are independent of each other, hydrogen; or Amino group, mono(C1-C) 10 Alkyl)amino group, di(C1-C 10 C1-C amino groups, or combinations thereof, substituted or unsubstituted. 10 It is also an alkyl group.

[0077] Furthermore, according to other concrete examples, in the above chemical formulas 5 and 6, Z 51 , Z 52 , Z 53 , R 51 , R 52 , R 53 , R 54 , R 61 and R 62 They are independent of each other, Hydrogen or amino group; or Amino group, mono(C1-C5 alkyl)amino group, di(C1-C5 alkyl)amino group, *-C(=O)-N(Q 51 )(Q 52 ), or any combination thereof, C1-C5 alkyl groups, substituted or unsubstituted; Q 51 and Q 52 They are independent of each other, hydrogen; or It is also a C1-C5 alkyl group that is substituted or unsubstituted with an amino group, a mono(C1-C5 alkyl)amino group, a di(C1-C5 alkyl)amino group, or a combination thereof.

[0078] Furthermore, according to other examples, the hydroxyl group-free nitrogen-containing compound may include the compound represented by the following chemical formula 51: <Chemical formula 51> T 52 -{[C(Z 51)(Z 52 )] a51 -N(Z 53 )} b51 -[C(Z 54 )(Z 55 )] a52 -T 51 In the aforementioned chemical formula 51, T 51 , T 52 , Z 51 , Z 52 and Z 53 The explanations relating to each are the same as those provided in this specification. Z 54 and Z 55 The explanations relating thereto are as follows in this specification. 51 This is the same as the explanation related to, a51 and a52 are independent integers between 2 and 5 (for example, 2 or 3). b51 is an integer between 1 and 7 (for example, 1, 2, or 3).

[0079] For example, in the above chemical formula 51, i) a51 and a52 are 2, and b51 is 1 (see, for example, compounds A1, A4, A28, etc.) ii) a51 and a52 are 2, and b51 is 2 (see, for example, compounds A5, A6, etc.) iii) a51 and a52 are 2, and b51 is 3 (see, for example, compound A2), iv) a51 and a52 are 3, and b51 is 2 (see, for example, compound A22), or v) a51 and a52 are 3, and b51 is also 1 (see, for example, compounds A23, A24, etc. below).

[0080] Furthermore, according to other examples, the hydroxyl group-free nitrogen-containing compound may include the compound represented by the following chemical formula 52: <Chemical formula 52> T 52 -[C(Z 51 )(Z 52 )] a53 -T51 In the aforementioned chemical formula 52, T 51 , T 52 , Z 51 and Z 52 The explanations relating to each are the same as those provided in this specification. a53 is an integer between 2 and 25, an integer between 2 and 20, an integer between 2 and 15, or an integer between 2 and 11.

[0081] For example, in the chemical formula 52, a53 is also an integer between 2 and 11.

[0082] As yet another example, in the aforementioned chemical formula 52, i) Is a53 11 (see, for example, compound A3), ii) a53 is 2 (see, for example, compounds A7, A8, A21, A27, etc.) or iii) a53 is also 6 (see, for example, compounds A9, A10, A11, etc.).

[0083] Furthermore, according to other embodiments, the hydroxyl group-free nitrogen-containing compound may include the compound represented by chemical formula 6.

[0084] For example, in the above chemical formula 6, i) L6 is a single bond, and a6 is 2 (see, for example, compounds A12 through A17, A20, etc.), ii) L6 is a single bond, and a6 is 1 (see compound A18, for example), iii) L6 is a single bond, and a6 is 3 (see, for example, compound A19), iv) L6 is a C3 alkylene group, and a6 is 2 (see, for example, compound A25), or v) L6 is a C3 alkylene group, and a6 is also 1 (see, for example, compound A26).

[0085] Furthermore, according to other embodiments, the hydroxyl group-free nitrogen-containing compound may include at least one of the following compounds A1 to A28:

[0086] [ka]

[0087] [ka]

[0088] The content (weight) of the etching modifier is as follows per 100 wt% of the composition: 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 It is also 0.05wt%~1wt%, 0.1wt%~5wt%, 0.1wt%~4wt%, 0.1wt%~3wt%, 0.1wt%~2wt%, 0.1wt%~1.5wt%, 0.1wt%~1wt%, 0.5wt%~5wt%, 0.5wt%~4wt%, 0.5wt%~3wt%, 0.5wt%~2wt%, 0.5wt%~1.5wt%, 0.5wt%~1wt%, or 1wt%~1.5wt%.

[0089] pH The aforementioned composition may have a pH of 2.0 or less. For example, the pH of the compositions described above may be 1.7 or less, 1.5 or less, 1.3 or less, 1.0 or less, 0.9 or less, 0.7 or less, 0.5 or less, 0.3 or less, 0.1 or less, or 0.0 or less.

[0090] For example, the compositions are -3.0~2.0, -3.0~1.7, -3.0~1.5, -3.0~1.3, -3.0~1.0, -3.0~0.9, -3.0~0.7, -3.0~0.5, -3.0~0, -2.5~2.0, -2.5~1.7, -2.5~1.5, -2.5~1.3, -2.5~1.0, -2.5~0.9, -2.5~0.7, -2.5~0.5, -3.0~0, -2.0~2.0, -2.0~1.7, -2.0~1.5, -2.0~1.3, -2.0~1.0, -2.0~0.9, -2.0~0.7, -2.0~0.5, -2.0~0, It may have a pH of -1.5 to 2.0, -1.5 to 1.7, -1.5 to 1.5, -1.5 to 1.3, -1.5 to 1.0, -1.5 to 0.9, -1.5 to 0.7, -1.5 to 0.5, -1.5 to 0, -1.0 to 2.0, -1.0 to 1.7, -1.0 to 1.5, -1.0 to 1.3, -1.0 to 1.0, -1.0 to 0.9, -1.0 to 0.7, -1.0 to 0.5, -1.0 to 0, -0.6 to 2.0, -0.6 to 1.7, -0.6 to 1.5, -0.6 to 1.3, -0.6 to 1.0, -0.6 to 0.9, -0.6 to 0.7, -0.6 to 0.5, or -0.6 to 0. The composition having a pH within the range described above allows for even smoother interaction between the etching modifier and the metal atoms in the metal-containing film.

[0091] According to one example, the composition may contain 0.001 wt% to 3 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 modifier.

[0092] According to other examples, the composition may contain 0.001 wt% to 3 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 modifier.

[0093] Furthermore, according to other embodiments, the composition may contain 0.001 wt% to 3 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 modifier.

[0094] In further embodiments, the composition may be used in metal-containing film processing steps, such as etching, cleaning, and polishing steps for metal-containing films. A description relating to the metal-containing film is provided herein.

[0095] Alternatively, the composition may also be used as an etching by-product remover, a post-etch by-product remover, an ashing by-product remover, a cleaning composition, a photoresist (PR) remover, an etching composition for the packaging process, a cleaning agent for the packaging process, a wafer adhesive remover, an etching solution (Etchant), a post-etch residue stripper, an ashing residue cleaner, a photoresist residue stripper, a CMP cleaner, or a post-CMP cleaner.

[0096] Method for treating metal-containing films Using the composition described above, a metal-containing film comprising a first region and a second region, wherein the substances contained in the first region and the substances contained in the second region are different from each other, can be effectively treated. For descriptions relating to the metal-containing film, the first region, and the second region, please refer to the provisions of this specification.

[0097] In one embodiment, the first and second regions may independently contain 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.

[0098] In other embodiments, 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.

[0099] In further embodiments, the first region may include a metal nitride, a metal oxynitride, or a combination thereof, and the second region may include a conductive metal.

[0100] In further embodiments, the first region comprises titanium nitrides, titan oxynitrides, or combinations thereof, each of which may optionally further include indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

[0101] Figures 1A and 12 are diagrams that briefly illustrate one example of a method for treating metal-containing films.

[0102] Referring to Figure 1A, a substrate 10 with a metal-containing film 20a is provided. Although not shown in Figure 1A, various circuit elements, for example, can be selectively placed between the substrate 10 and the metal-containing film 20a.

[0103] 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 arranged spaced apart from each other or partially or more in contact with each other, and the metal-containing film 20a may have a variety of patterns. The metal-containing film 20a including the first region 21 and the second region 22 may be brought into contact with composition 30 to remove a portion of the metal-containing film 20a. For example, during etching, cleaning and / or polishing processes of the metal-containing film 20a, the metal-containing film 20a may be brought into contact with composition 30. The composition 30 includes oxidizing agents, phosphoric acid, organic acids and etching modifiers as described herein, for a detailed description thereof, refer to what is provided herein.

[0104] According to one example, the etching rate ratio obtained by dividing the first etching rate at which composition 30 etches the first region 21 by the second etching rate at which composition 30 etches the second region 22 is 0.04 or greater. For example, the etching rate ratio obtained by dividing the first etching rate at which composition 30 etches the first region 21 by the second etching rate at which composition 30 etches the second region 22 is 0.05 or more, 0.06 or more, 0.04 to 1.0, 0.05 to 1.0, 0.06 to 1.0, 0.04 to 0.5, 0.05 to 0.5, 0.06 to 0.5, 0.04 to 0.3, 0.05 to 0.3, 0.06 to 0.3, 0.04 to 0.2, 0.05 to 0.2, 0.06 to 0.2, 0.04 to 0.15, 0.05 to 0.15, 0.06 to 0.15, or 0.06 to 0.13.

[0105] Figure 1B is a schematic diagram showing the surface of a metal-containing film 20a that may come into contact with composition 30, wherein the etching area ratio, obtained by dividing the first area of ​​the first region 21 exposed for contact with composition 30 by the second area of ​​the second region 22 exposed for contact with composition 30, is 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.

[0106] When the metal-containing film 20a comes into contact with the composition 30, the interaction of the oxidizing agent, phosphoric acid, organic acid, and etching modifier contained in the composition 30 controls the high reactivity of the metal contained in the metal-containing film 20a (for example, a metal such as molybdenum contained in the second region 22). As a result, the etching rate of the region containing the relatively highly reactive metal among the first region 21 and the second region 22 (for example, the etching rate of the second region 22) is appropriately controlled, and a portion of the first region 21 and a portion of the second region 22 are etched, forming a metal-containing film pattern 20 with a substantially flat surface (for example, with virtually no step difference between the first region 21 and the second region 22), as shown in Figure 2. After the contact step with the composition 30, virtually no by-products derived from the metal-containing film 20a (for example, metal oxides derived from the metal-containing film 20a, such as molybdenum oxide) remain on the surface of the metal-containing film pattern 20. For example, the presence or absence of residual by-products can be confirmed through TEM (Transmission Electron Microscope) analysis, SEM (Scanning Electron Microscope) analysis, etc.

[0107] Figures 3 and 4 are diagrams that briefly illustrate other concrete examples of the metal-containing film treatment method.

[0108] Referring to Figure 3, a substrate 10 is provided which, in addition to the metal-containing film 20a, has an additional material 40 positioned adjacent to the metal-containing film 20a. For explanations of the metal-containing film 20a and the substrate 10 in Figure 3, please refer to Figure 1A.

[0109] The additional substance 40 in Figure 3 is positioned at a distance from the metal-containing film 20a, or in partial or greater contact with it. In this specification, the additional substance 40 means a substance that is positioned adjacent to the metal-containing film 20a, in addition to the metal-containing film 20a, and is present in a region affected by composition 30 when the metal-containing film 20a is treated with composition 30.

[0110] The additional material 40 may include at least one of insulating materials and semiconductor materials. The insulating materials and semiconductor materials may include a variety of known materials.

[0111] 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 further optionally include Si, Ta, Ti, Zr, or any combination thereof. Further examples of insulating materials may include TEOS (tetraethyl orthosilicate), HSQ (hydrogen silsesquioxane), MSQ (methyl silsesquioxane), etc.

[0112] The semiconductor material may include, for example, as a material contained in a channel, a group IV semiconductor material such as silicon, germanium (Ge), silicon germanium (SiGe), silicon carbide (SiC), 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, and so on. 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.

[0113] As shown in Figure 3, the metal-containing film 20a, including the first region 21 and the second region 22, and the additional substance 40 may be brought into contact with composition 30, thereby removing a portion of the metal-containing film 20a. For example, during etching, cleaning, and / or polishing processes 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 composition 30. The composition 30 includes oxidizing agents, phosphoric acid, organic acids, and etching modifiers as described herein, for a detailed description thereof, refer to the foregoing.

[0114] 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 comes into contact with the composition 30, the interaction of the oxidizing agent, phosphoric acid, organic acid, and etching modifier contained in the composition 30 controls the high reactivity of the metal contained in the metal-containing film 20a (for example, a metal such as molybdenum contained in the second region 22). As a result, the etching rate of the region containing the relatively highly reactive metal among the first region 21 and the second region 22 (for example, the etching rate of the second region 22) is appropriately controlled, and a portion of the first region 21 and a portion of the second region 22 are etched, forming a metal-containing film pattern 20 with a substantially flat surface (for example, with virtually no step difference between the first region 21 and the second region 22), as shown in Figure 4. After the contact step with the composition 30, virtually no by-products derived from the metal-containing film 20a (for example, metal oxides derived from the metal-containing film 20a along with molybdenum oxide) remain on the surface of the metal-containing film pattern 20. Furthermore, for example, an additional material 40 comprising at least one of an insulating material and a semiconductor material is not substantially damaged by composition 30.

[0115] Manufacturing method of electronic components High-quality electronic devices can be fabricated using the compositions described above. Therefore, a method for manufacturing electronic devices using the compositions can be provided.

[0116] According to one embodiment, A method for manufacturing an electronic device including a transistor, The aforementioned transistor is Channels and The channel is electrically connected to a source and a drain, which are arranged at a distance from each other. Terminal gate and, A gate insulating film disposed between the gate electrode and the channel, Includes, The method for manufacturing the aforementioned electrical element is: A step of providing a barrier layer comprising a metal nitride, a metal oxynitride, or a combination thereof, The steps include providing a conductive layer containing a conductive metal, The steps include bringing the barrier layer and the conductive layer into contact with the composition, etching a portion of the barrier layer and a portion of the conductive layer to form the gate electrode, A method for manufacturing an electronic device is provided, including the following.

[0117] The channel may include, for example, the semiconductor materials 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. 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.

[0118] 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 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 further optionally include Si, Ta, Ti, Zr, or any combination thereof.

[0119] The gate electrode may include a barrier layer and a conductive layer. The barrier layer may be disposed, for example, between the gate insulating film and the conductive layer.

[0120] To provide the aforementioned gate electrode, a barrier layer and a conductive layer can be provided. For example, a conductive layer can be provided on the surface of the barrier layer after the barrier layer has been formed, but various modifications are possible, such as forming the barrier layer on the surface of the conductive layer after the conductive layer has been formed, depending on the structure of the channel and / or gate electrode.

[0121] The barrier layer may be provided to prevent peripheral diffusion of conductive metals (e.g., metal ions) contained in the conductive layer and / or to facilitate the smooth deposition of the conductive layer.

[0122] For a detailed description of each of the metal nitrides and / or metal oxynitrides contained in the barrier layer, refer to the descriptions of each of the metal nitrides and / or metal oxynitrides contained in the first region of the metal-containing film as provided herein.

[0123] In one embodiment, the barrier layer comprises a titanium nitride, a titan oxynitride, or a combination thereof, wherein each of the titanium nitride and titan oxynitride may further optionally comprise indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

[0124] A detailed explanation of the conductive metal contained in the conductive layer can be found in the explanation of the conductive metal contained in the second region of the metal-containing film as described herein.

[0125] According to one example, the conductive layer may contain tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

[0126] Next, the barrier layer and the conductive layer may be brought into contact with a composition as described herein, and a portion of the barrier layer and a portion of the conductive layer may be etched to form a gate electrode.

[0127] When the barrier layer and conductive layer come into contact with a composition as described herein, the interaction of the oxidizing agent, phosphoric acid, organic acid, and etching modifier contained in the composition controls the high reactivity of the conductive metal contained in the conductive layer. This appropriately controls the etching rate of the conductive layer, while a portion of the barrier layer and a portion of the conductive layer are etched, forming a gate electrode with a substantially flat surface (for example, with virtually no step difference between the barrier layer and the conductive layer). Furthermore, after the contact step with the composition, virtually no by-products (e.g., oxides of conductive metals) originating from the conductive layer remain on the gate electrode surface. Moreover, at least one of the channels and gate insulating films located adjacent to the gate electrode is not substantially damaged by the composition, and a high-quality electronic device including a gate electrode with a precise pattern can be fabricated without damaging the region adjacent to the gate electrode.

[0128] The aforementioned electronic element is also a semiconductor memory element.

[0129] For example, the electronic elements may include volatile memory elements such as DRAM (Dynamic Random Access Memory) elements or SRAM (static random access memory) elements, resistive random access memory (ReRAM) elements, electrically erasable programmable read-only memory (EEPROM) elements, flash memory (which can also be considered a subset of EEPROM) elements, ferroelectric random access memory (FRAM®) elements and magnetoresistive random access memory (MRAM) elements, and non-volatile memory elements such as other semiconductor elements capable of storing information.

[0130] According to one example, the aforementioned electronic element is also a DRAM element.

[0131] The manufacturing method of the electronic element will be described in more detail below with reference to Figures 5, 6A, 6B, 7, 8, and 9.

[0132] Figure 5 is a schematic plan view of an exemplary embodiment of the electronic element 3000, and Figure 6 is a perspective view of the electronic element 3000 shown in Figure 5. The electronic element 3000 in Figure 5 is also a DRAM element.

[0133] Referring to Figures 5, 6A, and 6B, the electronic element 3000 includes a plurality of unit elements 3100 arranged in an array. Here, each unit element 3100 has a 1T1C structure consisting of one transistor and one capacitor.

[0134] The electronic element 3000 includes a transistor structure 100 and a plurality of capacitors 3500 provided to the transistor structure 100. The transistor structure 100 may also be a vertical channel array transistor structure (see Figure 6A) including channels arranged perpendicular to the substrate, or a channel array transistor structure (see Figure 6B) including channels arranged and stacked horizontally to the substrate.

[0135] In the transistor structure 100, multiple gate electrodes (or word lines 150 and multiple bit lines 160) are provided so as to intersect each other. Each gate electrode 150 extends in a first direction (e.g., the x-axis direction), and each bit line 160 may extend in a second direction (e.g., the y-axis direction) intersecting the first direction. A transistor is positioned at the point where the multiple gate electrodes 150 and the multiple bit lines 160 intersect.

[0136] Figures 7 to 9 are diagrams that briefly illustrate part of the manufacturing process of the transistor structure 100 shown in Figure 6A.

[0137] The transistor structure 100 in Figure 7 includes a substrate 110 and a plurality of channels 140 arranged in an array on the substrate 110. Here, the plurality of channels 140 may be arranged in a two-dimensional array on the plane of the substrate 110 (for example, the xy plane).

[0138] The substrate 110 may, for example, contain silicon (Si). Specifically, the substrate 110 may consist of a silicon substrate doped with N-type impurities. However, this is merely illustrative, and the substrate 110 may also contain, for example, Group IV semiconductor materials such as 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.

[0139] Each of the multiple channels 140 may be provided extending vertically from the substrate 110. Here, each channel 140 may be provided projecting vertically from the upper surface of the substrate 110. Each channel 140 may contain the same semiconductor material as the semiconductor substrate 110 by being formed integrally with the substrate 110. In Figure 7, the channels 140 are formed integrally with the substrate 110, but various modifications are possible, such as the channels 140 being formed separately from the substrate 110.

[0140] 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 channel 140, and the drain (D) is provided to be connected to the top of channel 140. For example, the source (S) and drain (D) may be formed through doping region formation. The capacitor 3500 shown in Figure 5 may be connected to the drain (D) located at the top of channel 140.

[0141] On the upper surface of the substrate 110, sources (S) are provided in an array corresponding to the channels 140. Below these sources (S), a plurality of bit lines 160 extend 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 are formed inside the substrate 110 and may contain the same semiconductor material as the substrate 110. The bit lines 160 in Figure 7 can be formed separately using a material other than the substrate 110, and various modifications are possible.

[0142] Multiple insulating materials 170 may be provided in the substrate 110 between the multiple bit lines 160. The multiple insulating materials 170 can separate the multiple bit lines 160 into the interior of the substrate 110 by extending along a second direction aligned with the multiple bit lines 160. These insulating materials 170 may include, for example, silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, hafnium oxide, hafnium oxynitride, zirconium oxide, or combinations thereof.

[0143] A gate insulating film 130 is provided on the surface of the channel 140. The gate insulating film 130 may include insulating materials as described herein, such as silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, hafnium oxide, hafnium oxynitride, zirconium oxide, or combinations thereof.

[0144] As described above, in the substrate 110 provided with the channel 140 and gate insulating film 130, a barrier layer 151 containing a metal nitride, metal oxynitride, or a combination thereof and a conductive layer 152 containing a conductive metal are provided within the trench defined by the gate insulating film 130, as shown in Figure 7. For example, the conductive layer 152 can be provided on the surface of the barrier layer 151 after the barrier layer 151 has been formed, but various modifications are possible, such as forming the barrier layer 151 on the surface of the conductive layer 152 after the conductive layer 152 has been formed, depending on the structure of the channel 140 and / or gate electrode 150. For explanations of the metal nitride and / or metal oxynitride contained in the barrier layer 151 and the conductive metal contained in the conductive layer 152, please refer to the provisions herein.

[0145] Next, as shown in Figure 7, an embedded insulating layer 180 is provided within the trench defined in part or more by the conductive layer 152. The embedded insulating layer 180 serves to protect the gate electrode 150 in Figure 8 from penetration by oxygen and other elements. After the formation of the embedded insulating layer 180, a planarization process may be further performed as needed to expose the upper surfaces of the barrier layer 151 and the conductive layer 152.

[0146] Next, the exposed upper surfaces of the barrier layer 151 and the conductive layer 152 are brought into contact with composition 30, and a portion of the barrier layer 151 and a portion of the conductive layer 152 are etched to form a gate electrode 150 having a pattern as shown in Figure 8. In Figure 7, composition 30 comprises an oxidizing agent, phosphoric acid, organic acid, and etching modifier as described herein, for a detailed description thereof, refer to the foregoing.

[0147] The etching rate ratio obtained by dividing the first etching rate at which composition 30 etches the barrier layer 151 by the second etching rate at which composition 30 etches the conductive layer 152 is 0.04 or higher. For example, the etching rate ratio obtained by dividing the first etching rate at which composition 30 etches the barrier layer 151 by the second etching rate at which composition 30 etches the conductive layer 152 is 0.05 or more, 0.06 or more, 0.04 to 1.0, 0.05 to 1.0, 0.06 to 1.0, 0.04 to 0.5, 0.05 to 0.5, 0.06 to 0.5, 0.04 to 0.3, 0.05 to 0.3, 0.06 to 0.3, 0.04 to 0.2, 0.05 to 0.2, 0.06 to 0.2, 0.04 to 0.15, 0.05 to 0.15, 0.06 to 0.15, or 0.06 to 0.13.

[0148] On the other hand, the etching area ratio obtained by dividing the first area of ​​the barrier layer 151 exposed for contact with composition 30 by the second area of ​​the conductive layer 152 exposed for contact with composition 30 is also 0.05~1.0, 0.05~0.9, 0.05~0.7, 0.05~0.5, 0.05~0.4, 0.05~0.3, or 0.05~0.2.

[0149] When the barrier layer 151 and the conductive layer 152 come into contact with the composition 30, the interaction of the oxidizing agent, phosphoric acid, organic acid, and etching modifier contained in the composition 30 controls the high reactivity of the conductive metal contained in the conductive layer 152. As a result, the etching rate of the conductive layer 152 is appropriately controlled, and a portion of the barrier layer 151 and a portion of the conductive layer 152 are etched, forming a gate electrode 150 with a substantially flat upper surface (for example, there is substantially no step difference between the barrier layer 151 and the conductive layer 152), as shown in Figure 8. After the contact step with the composition 30, virtually no by-products (for example, oxides of conductive metals) originating from the conductive layer 152 remain on the surface of the gate electrode 150. Furthermore, the channel 140, gate insulating film 130, and embedded insulating layer 180, which are positioned adjacent to the gate electrode 150, are not substantially damaged by the composition 30, and a high-quality electronic device 3000 including a gate electrode 150 with a precise pattern can be fabricated without damaging the regions adjacent to the gate electrode 150, such as the channel 140, gate insulating film 130, and embedded insulating layer 180.

[0150] In Figure 8, the multiple gate electrodes 150 on the substrate 110 may be arranged to extend along a first direction (for example, the x-axis direction). The first direction may intersect with the second direction described above. For example, the first direction may be perpendicular to the second direction. However, it is not necessarily limited to these.

[0151] 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 serve as word lines.

[0152] Multiple gate electrodes 150 may be provided such that multiple insulating materials 170 provided below them intersect. The upper surface of the insulating material 170 may be provided adjacent to the lower surface of the gate electrode 150. Here, the upper part of the insulating material 170 may, but is not limited to, be provided so as to protrude from the bottom of the gate electrode 150.

[0153] Next, as shown in Figure 9, an insulating layer 190 may be further provided on the surface of the etched barrier layer 151 and the surface of the etched conductive layer 152. The insulating layer 190 serves to further insulate the gate electrode 150 from the channel 140 and may include, for example, an insulating material as described herein.

[0154] Electronic device manufacturing method Referring to Figure 10, one embodiment of an electronic device manufacturing method may include the steps of: preparing a substrate provided with a metal-containing film (S100); contacting the metal-containing film with a composition as described herein (S110); and fabricating an electronic element using subsequent steps 120. The subsequent steps may include a variety of known steps for fabricating an electronic element, such as a capacitor formation step.

[0155] Example 1 and Comparative Examples C1, C2, and C21 The substances weighed according to the content listed in Table 1 were mixed to prepare the compositions of Example 1 and Comparative Examples C1, C2, and C21, respectively. The remainder of each composition is water (deionized water).

[0156] Evaluation Example 1 The composition of Example 1 was placed in three separate beakers and heated to 60°C. Then, 1cm x 1cm specimens of titanium nitride-containing film, molybdenum film, and silicon oxide film were immersed in each beaker for 1 minute. The thicknesses of the titanium nitride-containing film, molybdenum film, and silicon oxide film were measured using an ellipsometer (M-2000, JAWoolam), a four-point resistance meter, and XRF (X-Ray Fluorescence Spectroscopy). The etching rate of the titanium nitride-containing film by the composition of Example 1 (also referred to as the "titanium nitride-containing film etching rate"), the etching rate of the molybdenum film by the composition of Example 1 (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 silicon oxide film by the composition of Example 1 (also referred to as the "silicon oxide film etching rate") were evaluated, and the results, along with the pH of Example 1, are summarized in Table 1. The unit for each etching rate is "A / min".

[0157] The above tests were repeated using compositions C1 and C2 respectively, and the results are summarized in Table 1.

[0158] For the composition of Comparative Example C21, in order to proceed with the evaluation in the same manner as in Evaluation Example 1, the compositions of Comparative Example C21 were placed in beakers and heated to 60°C. However, brown gas was generated from the beakers during heating, making it impossible to evaluate the etching rate of the titanium nitride-containing film, the molybdenum film, and the silicon oxide film of Comparative Example C21.

[0159] In Tables 1 through 5, "-" indicates "no evaluation value." Specifically, in Tables 1 through 5, "-" for etching rate indicates that the etching rate was too small to measure, meaning that almost no etching occurred.

[0160] [Table 1]

[0161] From Table 1, it can be seen that i) the composition of Comparative Example C1, which does not contain an oxidizing agent, was substantially unable to etch the titanium nitride-containing film and the molybdenum film, and ii) the composition of Comparative Example C2, which contains HF (hydrofluoric acid) as an oxidizing agent, was substantially unable to etch the titanium nitride-containing film and the molybdenum film and damaged the silicon oxide film. However, the composition of Example 1 was able to etch both the titanium nitride-containing film and the molybdenum film simultaneously at an appropriate etching ratio without substantially damaging the silicon oxide film, thus confirming that it can be usefully used for uniform etching of metal-containing films with diverse compositions.

[0162] On the other hand, it can be confirmed that the composition of Comparative Example C21 does not have sufficient stability to be effectively used for processing metal-containing films with diverse compositions.

[0163] Comparative Examples C3 to C5 and C31 The substances weighed according to the content listed in Table 2 were mixed to produce compositions C3, C5, and C31, respectively. The remainder of each composition is water (deionized water).

[0164] Evaluation Example 2 The pH, molybdenum film etching rate, and silicon oxide film etching rate of the composition of Comparative Example C3 were evaluated using the method described in Evaluation Example 1, and the results are summarized in Table 2. For comparison, the pH, molybdenum film etching rate, and silicon oxide film etching rate of the composition of Example 1 are also listed in Table 2.

[0165] The above tests were repeated using the composition of Comparative Example C31, and the results are summarized in Table 2.

[0166] On the other hand, in order to proceed with the evaluation of each of the compositions of Comparative Examples C4 and C5 in the same manner as in Evaluation Example 1, each of the compositions of Comparative Examples C4 and C5 was placed in a beaker and heated to 60°C. However, gas was generated in the beaker during heating, making it impossible to evaluate the etching rate of the molybdenum film and silicon oxide film of Comparative Examples C4 and C5.

[0167] [Table 2]

[0168] Table 2 confirms that the molybdenum film etching rates of the compositions of Comparative Examples C3 and C31, which do not contain phosphoric acid, are greater than those of the composition of Example 1. This confirms that the composition of Example 1 can etch the molybdenum film at an appropriate etching rate without substantially damaging the silicon oxide film, compared to the compositions of Comparative Examples C3 and C31, and can be usefully used for uniform etching of metal-containing films with diverse compositions.

[0169] On the other hand, it was confirmed that the compositions of Comparative Examples C4 and C5 did not possess sufficient stability to be effectively used for treating metal-containing films with diverse compositions.

[0170] Comparative example C6 The substances weighed according to the content listed in Table 3 as an oxidizing agent, inorganic acid, organic acid, and etching modifier were mixed to prepare the compositions of Comparative Example C6. The remainder of each composition corresponds to water (deionized water).

[0171] Evaluation Example 3 The pH, molybdenum film etching rate, and silicon oxide film etching rate of the composition of Comparative Example C6 were evaluated using the method described in Evaluation Example 1, and the results are summarized in Table 3. For comparison, the pH, molybdenum film etching rate, and silicon oxide film etching rate of the composition of Example 1 are also listed in Table 3.

[0172] [Table 3]

[0173] Table 3 confirms that the molybdenum film etching rate of the composition of Comparative Example C6, which does not contain acetic acid, is greater than that of the composition of Example 1. This confirms that the composition of Example 1 can etch the molybdenum film at an appropriate etching rate compared to the composition of Comparative Example C6, and can be usefully used for uniform etching of metal-containing films with diverse compositions.

[0174] Comparative examples C7~C12 The substances weighed according to the content listed in Table 4 as an oxidizing agent, inorganic acid, organic acid, and etching modifier were mixed to prepare the compositions of Comparative Examples C7 to C12. The remainder of each composition corresponds to water (deionized water).

[0175] Evaluation Example 4 For each of the compositions of Comparative Examples C7 to C12, the pH, molybdenum film etching rate, and silicon oxide film etching rate were evaluated using the method described in Evaluation Example 1, and the results are summarized in Table 4. For comparison, the pH, molybdenum film etching rate, and silicon oxide film etching rate of the composition of Example 1 are also listed in Table 4.

[0176] [Table 4]

[0177] From Table 4, it was confirmed that the molybdenum film etching rates of the composition of Comparative Example C7 that does not contain an etching regulator, the compositions of Comparative Examples C8 to C11 that contain a nitrogen-containing compound containing a hydroxy group as an etching regulator, and the composition of Comparative Example C12 that contains a nitrogen-free compound as an etching regulator are all higher than the molybdenum film etching rate of the composition of Example 1. Thus, it was confirmed that the composition of Example 1 can etch a molybdenum film at an appropriate etching rate, and can be usefully used for the uniform etching of metal-containing films having various compositions, as compared with each of the compositions of Comparative Examples C7 to C12.

[0178] Examples 2 to 4 An oxidizing agent, an inorganic acid, an organic acid, and substances weighed according to the contents described in Table 5 as an etching regulator were mixed to produce the compositions of Examples 2 to 4, respectively. The remainder of each composition corresponds to water (deionized water).

[0179] Evaluation Example 5 For each of the compositions of Examples 2 to 4, the pH, titanium nitride-containing film etching rate, molybdenum film etching rate, R, and silicon oxide film etching rate were evaluated by the method described in Evaluation Example 1, and the results are summarized in Table 5. The pH, titanium nitride-containing film etching rate, molybdenum film etching rate, R, and silicon oxide film etching rate of the composition of Example 1 are also described in Table 5.

[0180]

Table 5

[0181] From Table 5, it was confirmed that the compositions of Examples 2 to 4, like the composition of Example 1, can simultaneously etch a titanium nitride-containing film and a molybdenum film at an appropriate etching ratio without substantially damaging the silicon oxide film, and can be usefully used for the uniform etching of metal-containing films having various compositions.

[0182] Example 5 and Comparative Example C41 The substances weighed according to the content listed in Table 6 were mixed to prepare the compositions of Example 5 and Comparative Example C41, respectively. The remainder of each composition is water (deionized water). The weight-average molecular weight of PEI (polyethyleneimine) used as the etching modifier in Comparative Example C41 was 800 g / mol (n is an integer satisfying the weight-average molecular weight), and the PEI content in Table 6 indicates the solid content of PEI.

[0183] Evaluation Example 6 The compositions of Example 5 and Comparative Example C41 were placed in two separate beakers and heated to 60°C. ¹H NMR analysis was then performed on the compositions in each beaker. The structural changes of compounds A1 and PEI after mixing with high-concentration (70 wt%) phosphoric acid and high-temperature (60°C) heating were evaluated, and the results are summarized in Table 6. Furthermore, the ¹H NMR data of compound A1 after mixing with high-concentration (70 wt%) phosphoric acid and high-temperature (60°C) heating is shown in Figure 11A, and the ¹H NMR data of PEI after mixing with high-concentration (70 wt%) phosphoric acid and high-temperature (60°C) heating is shown in Figure 11B.

[0184] [Table 6]

[0185] Figures 6, 11A, and 11B show that after mixing with high-concentration (70 wt%) phosphoric acid and heating at high temperature (60°C), the structure of compound A1 remained substantially unchanged, while the structure of PEI was modified. This confirms that compound A1 can be used stably even under high-concentration (70 wt%) phosphoric acid and high-temperature (60°C) heating conditions, but PEI cannot be used stably under high-concentration (70 wt%) phosphoric acid and high-temperature (60°C) heating conditions.

[0186] Evaluation Example 7 Two 1cm × 1cm samples of Sample 1 were prepared, each containing a molybdenum film (see "M region" in Figure 12) and a titanium nitride-containing film (see "T region" in Figure 12) placed between two silicon oxide films (see "S1 region" and "S2 region" in Figure 12). Figure 12 shows the TEM (Transmission Electron Microscope) image of Sample 1.

[0187] Next, the compositions of Example 1 (using hydrogen peroxide as the oxidizing agent) and Comparative Example C2 (using HF as the oxidizing agent) were placed in two separate beakers and heated to 60°C. After that, Sample 1 was immersed in each beaker for 10 minutes, then rinsed with deionized water and dried to obtain Sample 1 immersed in each respective composition. The TEM image of Sample 1 immersed in the composition of Example 1 is shown in Figure 13A, and the TEM image of Sample 1 immersed in the composition of Comparative Example C2 is shown in Figure 13b.

[0188] In Figure 13A, a TEM image of Sample 1 immersed in the composition of Example 1, both the S1 and S2 regions, which are silicon oxide films, are observed. However, in Figure 13B, a TEM image of Sample 1 immersed in the composition of Comparative Example C2, the S1 region, which is the silicon oxide film on the left, is not observed, and it was confirmed that a considerable amount of the S2 region, which is the silicon oxide film on the right, has also disappeared.

[0189] This confirms that, unlike the composition of Comparative Example C2, the composition of Example 1 can be usefully used to treat various metal-containing films without substantially damaging the silicon oxide film adjacent to the metal-containing film. [Explanation of Symbols]

[0190] 10 circuit boards 20A metal-containing membrane 21 First area 22 Second area 20 Metal-containing film patterns 30 Composition 40 Additional substances 100 Transistor Structure 110 Substrate 130 Gate Insulating Film 140 Channel 151 Barrier Layer 152 Conductive Layer 150 Gate Electrode 160 Bit Line 170 Insulating Material 3000 Electronic Element 3100 Unit Element 3500 Capacitor S Source D Drain

Claims

1. A step of preparing a substrate provided with a metal-containing film including a first region and a second region, The step includes bringing the metal-containing film into contact with the composition, The first and second regions independently contain 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. The substances contained in the first region and the substances contained in the second region are different from each other. The composition comprises an oxidizing agent, phosphoric acid, an organic acid, and an etching controller. The oxidizing agent includes hydrogen peroxide, an iodine-containing compound, or a combination thereof. The etching modifier comprises a hydroxyl-free and nitrogen-containing compound. The hydroxyl group-free nitrogen-containing compound includes the compound represented by the following chemical formula 5, the compound represented by the following chemical formula 6, or a combination thereof. The composition has a pH of 2.0 or less. Method for treating a metal-containing film: <Chemical formula 5> T ５２ -[(L ５ ) ａ５ ]-T ５１ <Chemical formula 6> CY ６ -[L ６ -N(R ６１ )(R ６２ )] ａ６ In the aforementioned chemical formula 5, L ５ is *-C(Z ５１ ) (Z ５２ )-*', *-N(Z ５３ ) - *' or * - C (= O) - *', In the aforementioned chemical formula 5, a5 is an integer between 2 and 30. In the chemical formula 5, T ５１ is *-N(R ５１ ) (Caution ５２ ) and T ５２ is *-N(R ５３ ) (Caution ５４ ) and In the aforementioned chemical formula 6, ring CY ６ These are saturated or unsaturated carbon ring groups having 5 to 15 carbon atoms, saturated heterocyclic groups having 2 to 15 carbon atoms, pyridine groups, pyrimidine groups, pyrazine groups, pyridazine groups, triazine groups, carbazole groups, dibenzofuran groups, or dibenzothiophene groups. In the aforementioned chemical formula 6, L ６ is a single bond or C １ -C ３０ It is an alkylene group, In the aforementioned chemical formula 6, a6 is an integer from 1 to 5. In the aforementioned chemical formulas 5 and 6, Z ５１ Z ５２ Z ５３ , R ５１ , R ５２ , R ５３ , R ５４ , R ６１ and R ６２ They are independent of each other, Hydrogen or amino group; or amino group, mono(C) １ -C ３０ Alkyl)amino group, di(C) １ -C ３０ Alkyl)amino group, *-C(=O)-N(Q ５１ ) (Q ５２ ), or any combination thereof, C １ -C ３０ It is an alkyl group, Q ５１ and Q ５２ They are independent of each other, hydrogen; or amino group, mono(C) １ -C ３０ Alkyl)amino group, di(C) １ -C ３０ C １ -C ３０ It is an alkyl group, * and *' are bonding sites with adjacent atoms, respectively.

2. The first region includes titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), or any combination thereof. The method for treating a metal-containing film according to claim 1, wherein the second region includes tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

3. The method for treating a metal-containing film according to claim 1, wherein the first region includes a metal nitride, a metal oxynitride, or a combination thereof, and the second region includes a conductive metal.

4. The first region includes titanium nitride, titan oxynitride, or a combination thereof. The method for treating a metal-containing film according to claim 1, wherein each of the titanium nitride and titan oxynitride further selectively comprises indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

5. A method for treating a metal-containing film according to claim 1, wherein the etching area ratio obtained by dividing the first area exposed for contact with the composition in the first region by the second area exposed for contact with the composition in the second region is 0.05 to 1.

0.

6. The method for treating a metal-containing film according to claim 1, wherein the phosphoric acid content of the composition is 10 wt% to 85 wt% per 100 wt% of the composition.

7. In the above chemical formula 5, i) each L ５ is *-C(Z ５１ ) (Z ５２ ) - *', and a5 is an integer from 2 to 11, or ii) Each L ５ is *-C(Z ５１ ) (Z ５２ )-*' or *-N(Z ５３ ) - *', and a5 is an integer from 5 to 11, In the aforementioned chemical formula 6, ring CY ６ The method for treating a metal-containing film according to claim 1, wherein is a cyclopentane group, cyclohexane group, cycloheptane group, cyclooctane group, cyclopentene group, cyclohexene group, cycloheptene group, cyclooctene group, benzene group, naphthalene group, piperazine group, pyrrolidine group, piperidine group, azepane group, tetrahydrofuran group, tetrahydrothiophene group, tetrahydro-2H-pyran group, tetrahydro-2H-thiopyran group, 4H-pyran-4-one group, pyridine group, pyrimidine group, pyrazine group, pyridazine group, triazine group, carbazole group, dibenzofuran group, or dibenzothiophene group.

8. The method for treating a metal-containing film according to claim 1, wherein the composition has a pH of -3.0 to 1.

0.

9. A method for manufacturing an electronic device including a transistor, The aforementioned transistor is Channels and The channel is electrically connected to a source and a drain, which are arranged at a distance from each other. Terminal gate and, The gate insulating film is disposed between the gate electrode and the channel, The method for manufacturing the aforementioned electrical element is: A step of providing a barrier layer comprising a metal nitride, a metal oxynitride, or a combination thereof, The steps include providing a conductive layer containing a conductive metal, The steps include bringing the barrier layer and the conductive layer into contact with the composition, etching a portion of the barrier layer and a portion of the conductive layer to form the gate electrode, Includes, The composition comprises an oxidizing agent, phosphoric acid, an organic acid, and an etching controller. The oxidizing agent includes hydrogen peroxide, an iodine-containing compound, or a combination thereof. The etching modifier comprises a hydroxyl-free and nitrogen-containing compound. The hydroxyl group-free nitrogen-containing compound includes the compound represented by the following chemical formula 5, the compound represented by the following chemical formula 6, or a combination thereof. A method for manufacturing an electronic device, wherein the composition has a pH of 2.0 or less: <Chemical formula 5> T ５２ -[(L ５ ) ａ５ ]-T ５１ <Chemical formula 6> CY ６ -[L ６ -N(R ６１ )(R ６２ )] ａ６ In the aforementioned chemical formula 5, L ５ is *-C(Z ５１ ) (Z ５２ )-*', *-N(Z ５３ ) - *' or * - C (= O) - *', In the aforementioned chemical formula 5, a5 is an integer between 2 and 30. In the chemical formula 5, T ５１ is *-N(R ５１ ) (Caution ５２ ) and T ５２ is *-N(R ５３ ) (Caution ５４ ) and In the aforementioned chemical formula 6, ring CY ６ These are saturated or unsaturated carbon ring groups having 5 to 15 carbon atoms, saturated heterocyclic groups having 2 to 15 carbon atoms, pyridine groups, pyrimidine groups, pyrazine groups, pyridazine groups, triazine groups, carbazole groups, dibenzofuran groups, or dibenzothiophene groups. In the aforementioned chemical formula 6, L ６ is a single bond or C １ -C ３０ It is an alkylene group, In the aforementioned chemical formula 6, a6 is an integer from 1 to 5. In the aforementioned chemical formulas 5 and 6, Z ５１ Z ５２ Z ５３ , R ５１ , R ５２ , R ５３ , R ５４ , R ６１ and R ６２ They are independent of each other, Hydrogen or amino group; or an amino group, a mono(C １ -C ３０ -alkyl)amino group, a di(C １ -C ３０ -alkyl)amino group, *-C(=O)-N(Q ５１ )(Q ５２ ), or a combination thereof, a substituted or unsubstituted C １ -C ３０ -alkyl group; and Q ５１ and Q ５２ are, independently of each other, hydrogen; or amino group, mono(C) １ -C ３０ Alkyl)amino group, di(C) １ -C ３０ C １ -C ３０ Alkyl alkyl group; * and *' are bonding sites with adjacent atoms, respectively.

10. The barrier layer comprises titanium nitride, titan oxynitride, or a combination thereof. Each of the aforementioned titanium nitrides and titan oxynitrides further selectively comprises indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof. The method for manufacturing an electronic element according to claim 9, wherein the conductive layer comprises tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

11. The method for manufacturing an electronic element according to claim 9, further comprising the steps of bringing the barrier layer and the conductive layer into contact with the composition, etching a portion of the barrier layer and a portion of the conductive layer to form a gate electrode, and then providing an insulating layer to the surface of the etched barrier layer and the surface of the etched conductive layer.

12. It contains an oxidizing agent, phosphoric acid, organic acid, and an etching controller. The oxidizing agent includes hydrogen peroxide, an iodine-containing compound, or a combination thereof. The etching modifier comprises a hydroxyl-free and nitrogen-containing compound. The hydroxyl group-free nitrogen-containing compound includes the compound represented by the following chemical formula 5, the compound represented by the following chemical formula 6, or a combination thereof. A composition having a pH of 2.0 or less: <Chemical formula 5> T ５２ -[(L ５ ) ａ５ ]-T ５１ <Chemical formula 6> CY ６ -[L ６ -N(R ６１ )(R ６２ )] ａ６ In the aforementioned chemical formula 5, L ５ is *-C(Z ５１ ) (Z ５２ )-*', *-N(Z ５３ ) - *' or * - C (= O) - *', In the aforementioned chemical formula 5, a5 is an integer between 2 and 30. In the chemical formula 5, T ５１ is *-N(R ５１ ) (Caution ５２ ) and T ５２ is *-N(R ５３ ) (Caution ５４ ) and In the aforementioned chemical formula 6, ring CY ６ These are saturated or unsaturated carbon ring groups having 5 to 15 carbon atoms, saturated heterocyclic groups having 2 to 15 carbon atoms, pyridine groups, pyrimidine groups, pyrazine groups, pyridazine groups, triazine groups, carbazole groups, dibenzofuran groups, or dibenzothiophene groups. In the aforementioned chemical formula 6, L ６ is a single bond or C １ -C ３０ It is an alkylene group, In the aforementioned chemical formula 6, a6 is an integer from 1 to 5. In the aforementioned chemical formulas 5 and 6, Z ５１ Z ５２ Z ５３ , R ５１ , R ５２ , R ５３ , R ５４ , R ６１ and R ６２ They are independent of each other, Hydrogen or amino group; or amino group, mono(C) １ -C ３０ Alkyl)amino group, di(C) １ -C ３０ Alkyl)amino group, *-C(=O)-N(Q ５１ ) (Q ５２ ), or any combination thereof, C １ -C ３０ Alkyl alkyl group; Q ５１ and Q ５２ They are independent of each other, hydrogen; or amino group, mono(C) １ -C ３０ Alkyl)amino group, di(C) １ -C ３０ C １ -C ３０ Alkyl alkyl group; * and *' are bonding sites with adjacent atoms, respectively.

13. The composition according to claim 12, wherein the content of the oxidizing agent is 0.001 wt% to 3 wt% per 100 wt% of the composition.

14. The composition according to claim 12, wherein the content of the phosphoric acid is 10 wt% to 85 wt% per 100 wt% of the composition.

15. The composition according to claim 12, wherein the organic acid comprises a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, or any combination thereof.

16. The aforementioned organic acids 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, and salicylic acid. The composition according to claim 12, comprising an acid, or any combination thereof.

17. The composition according to claim 12, wherein the content of the organic acid is 0.1 wt% to 15 wt% per 100 wt% of the composition.

18. In the above chemical formula 5, i) each L ５ is *-C(Z ５１ ) (Z ５２ ) - *', and a5 is an integer from 2 to 11, or ii) Each L ５ is *-C(Z ５１ ) (Z ５２ )-*' or *-N(Z ５３ ) - *', and a5 is an integer from 5 to 11, In the aforementioned chemical formula 6, ring CY ６ The composition according to claim 12, wherein is a cyclopentane group, cyclohexane group, cycloheptane group, cyclooctane group, cyclopentene group, cyclohexene group, cycloheptene group, cyclooctene group, benzene group, naphthalene group, piperazine group, pyrrolidine group, piperidine group, azepane group, tetrahydrofuran group, tetrahydrothiophene group, tetrahydro-2H-pyran group, tetrahydro-2H-thiopyran group, 4H-pyran-4-one group, pyridine group, pyrimidine group, pyrazine group, pyridazine group, triazine group, carbazole group, dibenzofuran group, or dibenzothiophene group.

19. The composition according to claim 12, wherein the content of the etching modifier is 0.01 wt% to 5 wt% per 100 wt% of the composition.

20. The composition according to claim 12, having a pH of -3.0 to 1.0.

Images