Composition, method for treating a metal-containing film using the same, and method for manufacturing an electronic device using the same.

Abstract

The present invention provides a composition, a method for treating a metal-containing film using the same, and a method for manufacturing an electronic device using the same. [Solution] A composition comprising an oxidizing agent, an ammonium-based buffer, and an etching modifier, wherein the etching modifier comprises a compound represented by chemical formula 1; a method for processing a metal-containing film using the same; and a method for manufacturing an electronic device using the same. For a description of chemical formula 1, please refer to the one provided in this specification.

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 Art

[0002] In order to meet the excellent performance and low price required by consumers, an increase in the integration degree and an improvement in the reliability of electronic devices, such as semiconductor devices, are required. As the integration degree of semiconductor devices increases, damage to the components of semiconductor devices in the manufacturing process of semiconductor devices will have a greater impact on the reliability and electrical characteristics of semiconductor memory devices. In particular, in the manufacturing process of semiconductor devices, various processing steps, such as etching and cleaning steps, are performed on a predetermined film (for example, a metal-containing film). However, there is a continuous need for a composition having an appropriate etching rate and excellent cleaning ability for the effective performance of the metal-containing film processing step.

Summary of the Invention

Problems to be Solved by the Invention

[0003] The problem to be solved by the present invention is to provide a composition having an excellent etching selectivity and excellent cleaning ability, a method for treating a metal-containing film using the same, and a method for manufacturing an electronic device using the same.

Means for Solving the Problems

[0004] According to one aspect, it contains an oxidizing agent, an ammonium-based buffer, and an etching controller, and the composition provided contains a compound represented by Chemical Formula 1 as the etching controller:

Chemical Formula

[0005] In the Chemical Formula 1, R1 is C1-C 30 Alkyl or C2-C 30 It is an alkenyl group, R2~R7 are independent of each other, hydrogen, C1-C 30 Alkyl group, or C2-C 30 It is an alkenyl group, L1 and L2 are independent of each other, C1-C 30 Alkylene group or C2-C 30 It is an alkenylene group, X and Z are independently hydrogen, alkali metal, or ammonium groups. At least one of the methylene groups in R1 to R7 is optionally substituted with O or S. At least one of the hydrogen atoms contained in R1-R7, L1, and L2 is optionally a halogen atom, a hydroxyl group, a thiol group, or C1-C 30 Alkoxy group, or C1-C 30 It is substituted with an alkylthio group.

[0006] According to other embodiments, The steps include preparing a substrate to which a metal-containing film is provided, A method for processing a metal-containing film is provided, which includes the step of bringing the metal-containing film into contact with the composition.

[0007] The metals contained in the metal-containing film may include titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

[0008] During the contact step between the metal-containing film and the composition, a portion or more of the metal-containing film may be etched and cleaned.

[0009] The metal-containing film includes a first region and a second region. The second etching rate at which the composition etches the second region is greater than the first etching rate at which the composition etches the first region.

[0010] The first region comprises at least one of cobalt and copper, and the second region may comprise titanium nitride.

[0011] During the contact step between the metal-containing film and the composition, residues on the surface of the metal-containing film are removed, thereby cleaning a portion or more of the metal-containing film. The aforementioned residues may include etching gas residues, polymer residues, metal-containing residues, or any combination thereof.

[0012] In other embodiments, The steps include preparing a substrate to which a metal-containing film is provided, A step of bringing the metal-containing film and the composition into contact, A method for manufacturing an electronic element is provided, which includes the step of carrying out subsequent manufacturing processes to produce an electronic element. [Effects of the Invention]

[0013] The composition has an excellent etching selectivity and excellent cleaning ability, and can be effectively used in various processing steps for diverse metal-containing films, such as etching and cleaning. Therefore, by processing metal-containing films with the composition, high-quality electronic devices, such as semiconductor devices, can be manufactured. [Brief explanation of the drawing]

[0014] [Figure 1] This is a process flowchart of one embodiment of a method for fabricating electronic devices. [Figure 2] This figure briefly illustrates one embodiment of a method for treating metal-containing films. [Figure 3] This figure briefly illustrates one embodiment of a method for treating metal-containing films. [Figure 4A] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4B] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4C] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4D] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4E] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4F] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4G] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4H] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4I] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4J] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Modes for carrying out the invention]

[0015] metal-containing film The metals contained in the aforementioned metal-containing film include alkali metals (e.g., sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), etc.), alkaline earth metals (e.g., beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), etc.), lanthanide metals (e.g., lanthanum (La), europium (Eu), terbium (Tb), ytterbium (Yb), etc.), and transition metals (e.g., scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr)). This may include, for example, hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), nickel (Ni), copper (Cu), silver (Ag), zinc (Zn), etc., transition metals (e.g., aluminum (Al), gallium (Ga), indium (In), thallium (Tl), tin (Sn), bismuth (Bi), etc.), or any combination thereof.

[0016] According to one embodiment, the metal contained in the metal-containing film includes titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

[0017] According to another embodiment, the metal-containing film contains two or more different metals.

[0018] According to another embodiment, the metal contained in the metal-containing film is i) Titanium (Ti), and ii) containing indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

[0019] For example, the metal-containing film may include aluminum, titanium, lanthanum, cobalt, copper, or any combination thereof.

[0020] According to one embodiment, the metal-containing film contains titanium.

[0021] According to another embodiment, the metal-containing film contains cobalt.

[0022] In another embodiment, the metal-containing film contains copper.

[0023] In another embodiment, the metal-containing film includes titanium and cobalt.

[0024] In another embodiment, the metal-containing film includes titanium and copper.

[0025] The metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.

[0026] 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 comprises titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

[0027] According to other embodiments, the metal-containing film includes the metal nitride described above.

[0028] In yet another embodiment, the metal-containing film includes the aforementioned metals (for example, at least one of cobalt and copper).

[0029] In yet another embodiment, the metal-containing film comprises a metal nitride and a metal (for example, at least one of cobalt and copper). For example, the metal contained in the metal nitride and the metal are different from each other.

[0030] In yet another embodiment, the metal-containing film comprises a metal nitride and a metal (for example, at least one of cobalt and copper), wherein the metal contained in the metal nitride includes indium, titanium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof.

[0031] In yet another embodiment, the metal-containing film comprises a titanium nitride and a metal (for example, at least one of cobalt and copper), wherein the titanium nitride may further optionally further comprise indium, aluminum, lanthanum, scandium, gallium, hafnium, zinc, tungsten, silicon, or any combination thereof.

[0032] Further embodiments include titanium nitride, titanium nitride further containing aluminum (e.g., titanium / aluminum nitride or TiAlN), titanium nitride further containing lanthanum, and the like.

[0033] As yet another example, the metal-containing film includes a metal oxide. The metals included in the metal oxide include titanium, aluminum, lanthanum, scandium, gallium, hafnium, or any combination thereof. For example, the metal-containing film includes aluminum oxide (e.g., Al2O3), IGZO (indium gallium zinc oxide), and the like.

[0034] As yet another example, the metal-containing film includes the metal nitride and the metal oxide.

[0035] As yet another example, the metal-containing film may further contain, in addition to metals, metalloids (e.g., boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), etc.), nonmetals (e.g., nitrogen (N), phosphorus (P), oxygen (O), sulfur (S), selenium (Se), etc.), and any combination thereof.

[0036] For example, the metal-containing film may further contain silicon oxide.

[0037] According to one embodiment, the metal-containing film is a)i) Titanium nitride, or ii) Titanium nitride further comprising indium, aluminum, lanthanum, scandium, gallium, hafnium, zinc, tungsten, silicon, or any combination thereof, and b) Containing at least one of cobalt and copper.

[0038] The metal-containing film is a single-layer structure containing one or more substances, or a multilayer structure containing different substances. The multiple films included in the multilayer structure may be stacked vertically or arranged horizontally. The single-layer and multilayer structures can have a variety of 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 second etching rate at which the composition etches the second region is greater than the first etching rate at which the composition etches the first region. In a processing step for the metal-containing film (e.g., etching, cleaning, etc.), at least a portion of the first region and at least a portion of the second region are in contact with the composition, and since the second etching rate is greater than the first etching rate, the second region is etched faster than the first region. The first region and the second region may be arranged spaced apart from each other.

[0040] For example, the first region includes a metal, a metal oxide (e.g., aluminum oxide), a silicon oxide, or any combination thereof.

[0041] According to one embodiment, the first region includes at least one of cobalt and copper.

[0042] As another example, the second region includes metal nitrides (e.g., titanium nitrides).

[0043] As yet another example, the second region includes i) titanium nitride, ii) titanium nitride (e.g., TiAlN) further comprising indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) combinations thereof.

[0044] As yet another example, each of the first and second regions includes i) titanium nitride, ii) titanium nitride further comprising indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof.

[0045] As yet another example, the first region contains at least one of cobalt and copper, while the second region does not contain cobalt or copper.

[0046] As yet another example, the first region comprises at least one of cobalt and copper, and the second region comprises i) titanium nitride, ii) titanium nitride (e.g., TiAlN) further comprising indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof.

[0047] As yet another example, the first region comprises at least one of cobalt and copper, and the second region comprises titanium nitride, titanium nitride further comprising aluminum (e.g., TiAlN), or any combination thereof.

[0048] As yet another example, the first region includes at least one of a cobalt film and a copper film, and the second region includes a titanium nitride film, a titanium nitride film further containing aluminum (e.g., a titanium / aluminum nitride film or a TiAlN film), or any combination thereof.

[0049] As yet another example, the first region is a cobalt film, a copper film, or a combination thereof, and the second region is a titanium nitride film or a titanium nitride film further containing aluminum (e.g., a titanium / aluminum nitride film or a TiAlN film).

[0050] In this specification, etching of any film means that some or more of the material constituting the film is removed.

[0051] composition The aforementioned composition may include an oxidizing agent, an ammonium-based buffer, and an etching modifier.

[0052] 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.

[0053] The composition may further contain water. The composition may further contain a chelating agent, such as ethylenediaminetetraacetic acid (EDTA).

[0054] Oxidizing agent The oxidizing agent plays a role in etching a portion or more of the metal in the metal-containing film by oxidizing a portion or more of the metal in the metal-containing film to form a water-soluble complex, and includes, for example, at least one of hydrogen peroxide, nitric acid, and ammonium sulfate.

[0055] According to one embodiment, the oxidizing agent includes hydrogen peroxide.

[0056] In other embodiments, the oxidizing agent is hydrogen peroxide.

[0057] The content (weight) of the oxidizing agent is, for example, 16 wt% to 50 wt%, 18 wt% to 50 wt%, 20 wt% to 50 wt%, 22 wt% to 50 wt%, 25 wt% to 50 wt%, 16 wt% to 45 wt%, 18 wt% to 45 wt%, 20 wt% to 45 wt%, 22 wt% to 45 wt%, 25 wt% to 45 wt%, 16 wt% to 40 wt%, 18 wt% to 40 wt%, 20 wt% to 40 wt%, and 22 wt% to 40 wt% per 100 wt% of the composition. The values ​​are 25wt%~40wt%, 16wt%~35wt%, 18wt%~35wt%, 20wt%~35wt%, 22wt%~35wt%, 25wt%~35wt%, 16wt%~30wt%, 18wt%~30wt%, 20wt%~30wt%, 22wt%~30wt%, 25wt%~30wt%, 16wt%~27wt%, 18wt%~27wt%, 20wt%~27wt%, 22wt%~27wt%, or 25wt%~27wt%.

[0058] When the content range of the oxidizing agent satisfies the range described above, the composition can simultaneously have an excellent etching selectivity ratio and excellent cleaning ability.

[0059] Ammonium-based buffer The ammonium-based buffer can play a role in maintaining a high concentration of negative ions generated from the oxidizing agent, and in stabilizing the water-soluble composite formed when the negative ions oxidize a portion or more of the metal in the metal-containing film. By using such an ammonium-based buffer, a portion or more of the metal-containing film can be effectively etched.

[0060] The ammonium-based buffer contains an ammonium group.

[0061] According to one embodiment, the ammonium-based buffer contains an ammonium group represented by N(A 11 )(A 12 )(A 13 )(A 14 ), and the A 11 ~A 14 are, independently of each other, hydrogen, a C1-C 30 alkyl group, a C2-C 30 alkenyl group, a C3-C 30 carbocyclic group, or a C1-C 30 heterocyclic group.

[0062] For example, the A 11 ~A 14 are, independently of each other, hydrogen or a C1-C 10 alkyl group.

[0063] According to other embodiments, the ammonium buffer is a hydroxide, acetate, bicarbonate, benzoate, carbonate, formate, nitrate, hydrogensulfate, carbamate, sulfamate, citrate, phosphate, or sulfite. It comprises at least one of the following: ite, sulfobenzoate, oxalate, lactate, tartrate, dihydrogencitrate, glutamate, salicylate, bioxalate, octanoate, propionate, glycolate, and gluconate.

[0064] In another embodiment, the ammonium buffer comprises a phosphate or a hydroxide.

[0065] In another embodiment, the ammonium buffer comprises at least one of the following: a phosphate-containing ammonium compound (for example, at least one of the compounds represented by chemical formula 11-1, chemical formula 11-2, and chemical formula 11-3) and a hydroxide-containing ammonium compound (for example, the compound represented by chemical formula 11-4).

[0066] In another embodiment, the ammonium buffer comprises the phosphate-containing ammonium compound.

[0067] In another embodiment, the ammonium buffer comprises at least one of the compounds represented by chemical formula 11-1, chemical formula 11-2, chemical formula 11-3, and chemical formula 11-4: <Case 11-1> [N(A 11 )(A 12 )(A 13 )(A 14 )3PO4 <C11-2> [N(A 11 )(A 12 )(A 13 )(A 14 )]2HPO4 <C11-3> [N(A 11 )(A 12 )(A 13 )(A 14 )]H2PO4 <C11-4> [N(A 11 )(A 12 )(A 13 )(A 14 )]OH In the above chemical formulas 11-1 to 11-4, A 11 ~A 14 The descriptions relating to each of these are the same as those provided in this specification.

[0068] In further embodiments, the ammonium buffer comprises at least one of ammonium phosphate ((NH4)3PO4), diammonium monohydrogen phosphate ((NH4)2HPO4), ammonium dihydrogen phosphate ((NH4)H2PO4), [N(CH3)4]3PO4, bis(tetramethylammonium) monohydrogen phosphate ([N(CH3)4]2HPO4), tetramethylammonium dihydrogen phosphate ([N(CH3)4]H2PO4), ammonium hydroxide, and tetramethylammonium hydroxide (TMAH).

[0069] The content (by weight) of the ammonium-based buffer is, for example, 0.01 wt% to 10 wt%, 0.05 wt% to 10 wt%, 0.1 wt% to 10 wt%, 0.3 wt% to 10 wt%, 0.5 wt% to 10 wt%, 0.01 wt% to 7 wt%, 0.05 wt% to 7 wt%, 0.1 wt% to 7 wt%, 0.3 wt% to 7 wt%, 0.5 wt% to 7 wt%, and 0.01 wt% to 4 wt% per 100 wt% of the composition. These are 0.05wt%~4wt%, 0.1wt%~4wt%, 0.3wt%~4wt%, 0.5wt%~4wt%, 0.01wt%~2wt%, 0.05wt%~2wt%, 0.1wt%~2wt%, 0.3wt%~2wt%, 0.5wt%~2wt%, 0.01wt%~1wt%, 0.05wt%~1wt%, 0.1wt%~1wt%, 0.3wt%~1wt%, or 0.5wt%~1wt%.

[0070] According to one embodiment, the ammonium buffer comprises the phosphate-containing ammonium compound, the hydroxide-containing ammonium compound, or a combination thereof, wherein the content (weight) of the phosphate-containing ammonium compound and the content (weight) of the hydroxide-containing ammonium compound are, for example, 0.01 wt% to 10 wt%, 0.05 wt% to 10 wt%, 0.1 wt% to 10 wt%, 0.3 wt% to 10 wt%, 0.5 wt% to 10 wt%, 0.01 wt% to 7 wt%, 0.05 wt% to 7 wt%, 0.1 wt% to 7 wt%, 0.3 wt% to 7 wt%, and 0.5 wt% per 100 wt% of the composition. ~7wt%, 0.01wt%~4wt%, 0.05wt%~4wt%, 0.1wt%~4wt%, 0.3wt%~4wt%, 0.5wt%~4wt%, 0.0 1wt%~2wt%, 0.05wt%~2wt%, 0.1wt%~2wt%, 0.3wt%~2wt%, 0.5wt%~2wt%, 0.01wt%~1wt% These are 0.05wt%~1wt%, 0.1wt%~1wt%, 0.3wt%~1wt%, 0.5wt%~1wt%, 0.01wt%~0.7wt%, 0.05wt%~0.7wt%, 0.1wt%~0.7wt%, 0.3wt%~0.7wt%, 0.5wt%~0.7wt%, or 0.3wt%~0.5wt%.

[0071] When the content range of the ammonium-based buffer satisfies the range described above, the composition can simultaneously possess excellent etching selectivity and excellent cleaning ability.

[0072] Etching modifier The etching modifier can interact with various metal atoms in the metal-containing film being processed, thereby regulating the etching rate and other parameters. Furthermore, the etching modifier can remove residues generated during the metal-containing film deposition process and / or patterning process.

[0073] The etching modifier includes a compound represented by the following chemical formula 1: [ka]

[0074] In the aforementioned chemical formula 1, R1 is C1-C 30 Alkyl or C2-C 30 It is an alkenyl group, R2~R7 are independent of each other, hydrogen, C1-C 30 Alkyl group, or C2-C 30 It is an alkenyl group, L1 and L2 are independent of each other, C1-C 30 Alkylene group or C2-C 30 It is an alkenylene group, X and Z are independently hydrogen, alkali metal, or ammonium groups. At least one of the methylene groups in R1 to R7 is optionally substituted with O or S. At least one of the hydrogen atoms contained in R1-R7, L1, and L2 is optionally a halogen atom, a hydroxyl group, a thiol group, or C1-C 30 Alkoxy group, or C1-C 30 It is substituted with an alkylthio group.

[0075] The two *-C(=O)O- groups in Chemical Formula 1 can form strong bonds (see the two "2a"s in Chemical Formula 1') with the metal M (e.g., cobalt, copper, etc.) contained in the metal-containing film 2 in aqueous solution, so the compound represented by Chemical Formula 1 can be effectively fixed to the surface of the metal-containing film 2. Furthermore, the monoamine-based molecule having R1~R7, L1, and L2 as defined above (see "2b" in Chemical Formula 1') can have a relatively bulky structure because all three groups bonded to the N contained therein have "two or more carbon atoms". As a result, the compound represented by Chemical Formula 1 can provide a protective film with excellent surface properties on the surface of the metal-containing film 2, with intermolecular internal reactions (interactions) by the compound represented by Chemical Formula 1 substantially suppressed. Therefore, by using a composition containing the compound represented by Chemical Formula 1, the etching rate can be selectively adjusted by the metal of the metal-containing film, and at the same time, residues generated during the metal-containing film deposition process and / or patterning process can be effectively removed.

[0076] [ka]

[0077] Furthermore, the compound represented by chemical formula 1 does not substantially form micelles and, at the same time, dissolves substantially uniformly in the composition, thereby substantially preventing bubble formation and phase separation during the manufacture of the composition and / or the processing of metal-containing films using the composition. Bubble formation and phase separation in the composition can lead to reduced efficiency and stability of the metal-containing film processing process, wafer damage, residue regeneration, and contamination of various equipment; therefore, it is necessary to prevent bubble formation and phase separation during the manufacture of the composition and / or the processing of metal-containing films using the composition. Although not limited by any particular theory, compositions in which bubble formation and / or phase separation are observed during and / or immediately after manufacture are substantially unsuitable for processing metal-containing films because this interferes with uniform contact between other active ingredients in the composition and the metal-containing film, and generates further residues on the surface of the metal-containing film. Therefore, by using a composition containing the compound represented by chemical formula 1, the etching rate can be selectively adjusted by the metal of the metal-containing film without bubble formation and phase separation, and at the same time, residues generated during the metal-containing film formation process and / or patterning process can be effectively removed.

[0078] According to one embodiment, in the chemical formula 1, R1 is 1) C3-C 30 Alkyl or C3-C 30 Is it an alkenyl group? 2) C5-C 30 Alkyl or C5-C 30 Is it an alkenyl group? 3) C7-C 30 Alkyl or C7-C 30 Is it an alkenyl group? 4) C3-C 20 Alkyl or C3-C 20 Is it an alkenyl group? 5) C5-C 20 Alkyl or C5-C 20 Is it an alkenyl group? 6) C7-C 20 Alkyl or C7-C 20 Is it an alkenyl group? 7) C3-C 11 Alkyl or C3-C 11 Is it an alkenyl group? 8) C5-C 11 Alkyl or C5-C 11 It is an alkenyl group, or 9) C7-C 11 Alkyl or C7-C 11 It is an alkenyl group.

[0079] In another embodiment, in the chemical formula 1, the atoms contained in R1 are carbon and hydrogen. In the chemical formula 1, when the atoms contained in R1 are carbon and hydrogen (for example, when R1 is unsubstituted C1-C 30 Alkyl or unsubstituted C2-C 30 (In the case of an alkenyl group), the hydrophobicity of the protective film provided on the surface of the metal-containing film 2 by chemical formula 1 is further improved, and side reactions of the metal-containing film in contact with the composition (e.g., surface oxidation of the metal-containing film) can be substantially prevented.

[0080] In another embodiment, in the chemical formula 1, R2 to R7 are independent of each other. i) Hydrogen, C1-C 20 Alkyl group, or C2-C 20 Is it an alkenyl group? ii) Hydrogen, C1-C 10 Alkyl group, or C2-C 10 Is it an alkenyl group? iii) Hydrogen, C1-C5 alkyl group, or C2-C5 alkenyl group, iv) It is a hydrogen or methyl group, or v) It is hydrogen.

[0081] In another embodiment, in the chemical formula 1, L1 and L2 are independent of each other. i) C1-C 10 Is it an alkylene group? ii) Is it a C1-C4 alkylene group? iii) It is a C1-C2 alkylene group, or iv) It is a C1 alkylene group (methylene group).

[0082] In another embodiment, in the chemical formula 1, the atoms contained in L1 and L2 are carbon and hydrogen. In the case where the atoms contained in L1 and L2 in the chemical formula 1 are carbon and hydrogen (for example, when L1 and L2 are each unsubstituted C1-C 30 Alkylene group or unsubstituted C2-C 30 (In the case of an alkenylene group), the hydrophobicity of the protective film provided on the surface of the metal-containing film 2 by chemical formula 1 is further improved, and side reactions of the metal-containing film in contact with the composition (e.g., surface oxidation of the metal-containing film) can be substantially prevented.

[0083] In another embodiment, in the chemical formula 1, X and Z are independently hydrogen, Na, K, or N(A1)(A2)(A3)(A4), and A1 to A4 are independently hydrogen, C1-C 30 Alkyl alkyl group, C2-C 30 Alkenyl group, C3-C 30 Carbon ring group, or C1-C 30 It is a heterocyclic group. For example, A1 to A4 are independently of each other, either hydrogen or C1-C 10 It is an alkyl group.

[0084] In another embodiment, in the chemical formula 1, at least one of the methylene groups (for example, one or two methylene groups) included in R1 to R7 is optionally substituted with O or S.

[0085] In further embodiments, in the chemical formula 1, at least one of the hydrogen atoms contained in R1-R7, L1 and L2 is selectively a halogen atom (e.g., -F, -Cl, -Br, etc.), a hydroxyl group, a thiol group, or C1-C 30 Alkoxy groups (e.g., C1-C 10 Alkoxy group), or C1-C 30Alkylthio group (e.g., C1-C 10 It is substituted with an alkylthio group.

[0086] In another embodiment, the etching modifier comprises at least one of the following compounds 1 and 2: [ka]

[0087] Furthermore, according to other embodiments, the content of the etching modifier is, per 100 wt% of the composition, 0.001 wt% to 10 wt%, 0.01 wt% to 10 wt%, 0.1 wt% to 10 wt%, 0.2 wt% to 10 wt%, 0.001 wt% to 5 wt%, 0.01 wt% to 5 wt%, 0.1 wt% to 5 wt%, 0.2 wt% to 5 wt%, and 0.001 wt%~1wt%, 0.01wt%~1wt%, 0.1wt%~1wt%, 0.2wt%~1wt%, 0.001wt%~0.5wt%, 0.01wt%~0.5wt%, 0.1wt%~0.5wt%, 0.2wt%~0.5wt%, 0.001wt%~0.2wt%, 0.01wt%~0.2wt%, or 0.1wt%~0.2wt%.

[0088] The pH of the compositions described above is 1.0-12.0, 3.0-12.0, 5.0-12.0, 7.0-12.0, 1.0-10.0, 3.0-10.0, 5.0-10.0, 7.0-10.0, 3.0-8.0, 5.0-8.0, or 7.0-8.0. Having a pH within the above range allows for smoother interaction between the etching modifier and the metal atoms in the metal-containing film.

[0089] According to one embodiment, the composition can be used in metal-containing film processing steps, such as etching and cleaning steps for metal-containing films. A description of the metal-containing film is provided herein.

[0090] Alternatively, the composition can 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 etchant, a post-etch residue stripper, an ashing residue cleaner, a photoresist residue stripper, or a post-CMP cleaner.

[0091] Method for treating metal-containing films and method for manufacturing electronic devices Metal-containing films can be effectively treated using the compositions described above.

[0092] Referring to Figure 1, one embodiment of the method for processing the metal-containing film includes the steps of preparing a substrate to which the metal-containing film is provided (S100) and bringing the metal-containing film into contact with a composition as described herein (S110).

[0093] For a description of the aforementioned metal-containing film, please refer to the one provided in this specification.

[0094] For example, the metals contained in the metal-containing film include titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

[0095] As yet another example, the metal-containing film includes a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.

[0096] As yet another example, 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 includes titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

[0097] As yet another example, the metal-containing film includes titanium nitride.

[0098] As yet another example, the metal-containing film includes at least one of cobalt and copper.

[0099] According to one embodiment, a portion or more of the metal-containing film may be etched and cleaned during the contact step between the metal-containing film and the composition.

[0100] In the above composition, i) the oxidizing agent plays a role in etching a portion or more of the metal-containing film by oxidizing a portion or more of the metal in the metal-containing film to form a water-soluble complex; ii) the ammonium buffer plays a role in maintaining a high concentration of negative ions generated from the oxidizing agent and stabilizing the water-soluble complex formed by the negative ions oxidizing a portion or more of the metal in the metal-containing film, thereby effectively etching a portion or more of the metal-containing film; and iii) the compound represented by chemical formula 1 contained in the etching modifier has two *-C(=O)O- groups, enabling strong bonding with the metal contained in the metal-containing film (e.g., cobalt, copper, etc.), and has a monoamine-based molecule having R1~R7, L1 and L2 as defined herein, providing a protective film on the surface of the metal-containing film with excellent surface properties in which intermolecular internal reactions (interactions) are substantially suppressed, and further improving hydrophobicity. By using an etching modifier containing a compound represented by such chemical formula 1, the etching rate can be selectively controlled depending on the metal in the metal-containing film, and at the same time, residues generated during the metal-containing film deposition process and / or patterning process can be effectively removed. Therefore, the aforementioned compositions can be usefully used in a variety of processing steps for the metal-containing film.

[0101] Figures 2 and 3 are diagrams that briefly illustrate one embodiment of a method for processing metal-containing films.

[0102] Referring to Figure 2, a substrate 10 is provided on which a metal-containing film 20 is provided. An intermediate layer 11 is placed between the substrate 10 and the metal-containing film 20. Although not shown in Figure 2, circuit elements (e.g., transistor gates, metal lines), impurity regions, and semiconductor layers may be placed inside the substrate 10, on top of the substrate 10, and / or between the substrate 10 and the intermediate layer 11. In one embodiment, the metal-containing film 20 is placed directly on the substrate 10, and the intermediate layer 11 is optional.

[0103] The metal-containing film 20 includes 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 some or more of them may be in contact with each other, and the metal-containing film 20 can have a variety of three-dimensional patterns. The second etching rate at which the composition etches the second region 22 is greater than the first etching rate at which the composition etches the first region 21. For example, the first etching rate is 0, and the first region 21 is not etched.

[0104] Referring to Figure 3, the composition can be used to etch the metal-containing film 20 to etch a portion or more of the second region 22 and form a metal-containing film pattern 25. The etching process is carried out by bringing a portion or more of the first region 21 and a portion or more of the second region 22 into contact with the composition.

[0105] The composition can etch only a portion or more of the second region 22 without etching the first region 21. Alternatively, the composition can etch a portion or more of the first region 21 and a portion or more of the second region 22, respectively. In Figure 3, the metal-containing film pattern 25 formed after etching includes a portion or more of the second region 22, but various modifications are possible, such as performing the etching process to completely remove the second region 22 from the metal-containing film pattern 25 as needed.

[0106] According to another embodiment, the first region 21 includes at least one of cobalt and copper.

[0107] In yet another embodiment, the second region 22 includes a metal nitride (for example, titanium nitride).

[0108] In further embodiments, the second region 22 includes i) a titanium nitride, ii) a titanium nitride (e.g., TiAlN) further comprising indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof.

[0109] In further embodiments, each of the first region 21 and the second region 22 comprises i) titanium nitride, ii) titanium nitride further comprising indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof.

[0110] As yet another example, the first region 21 contains at least one of cobalt and copper, while the second region 22 does not contain cobalt or copper.

[0111] As yet another example, the first region 21 comprises at least one of cobalt and copper, and the second region 22 comprises i) titanium nitride, ii) titanium nitride (e.g., TiAlN) further comprising indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof.

[0112] As yet another example, the first region 21 includes at least one of cobalt and copper, and the second region 22 includes titanium nitride (TiN), titanium nitride further containing aluminum (e.g., TiAlN), or any combination thereof.

[0113] As yet another example, the first region 21 includes at least one of a cobalt film and a copper film, and the second region 22 includes a titanium nitride film (TiN film), a titanium nitride film further containing aluminum (e.g., a titanium / aluminum nitride film or a TiAlN film), or any combination thereof.

[0114] As yet another example, the first region 21 is a cobalt film, and the second region 22 is a titanium nitride film (TiN film) or a titanium nitride film further containing aluminum (e.g., a titanium / aluminum nitride film or a TiAlN film).

[0115] As yet another example, the first region 21 is a copper film, and the second region 22 is a titanium nitride film (TiN film) or a titanium nitride film further containing aluminum (e.g., a titanium / aluminum nitride film or a TiAlN film).

[0116] As yet another example, the contact step between the metal-containing film 20 and the composition removes the residue R on the surface of the metal-containing film 20, thereby cleaning a portion or more of the metal-containing film 20 and forming a metal-containing film pattern 25 without any residue R remaining, as shown in Figure 3.

[0117] The residue R is a by-product generated during the deposition and / or patterning of the metal-containing film 20, and is a substance that remains on the surface of the metal-containing film 20 and / or the metal-containing film pattern 25, causing increased electrical resistance and / or electrical short circuits between electrical wiring. The residue R is an etching residue generated as a result of etching, and includes, for example, etching gas residue, polymer residue, metal-containing residue, or any combination thereof.

[0118] The etching gas residue is a residue derived from the etching gas used in dry etching. The etching gas is, for example, carbon fluoride gas. For example, the etching gas includes CHF3, C2F6, CF4, C4F8, C2HF5, etc. The etching gas residue includes reaction products of the etching gas itself and / or any substance that came into contact with the etching gas during the etching process using the etching gas.

[0119] The polymer residue is a polymer derived from various organic materials contained in the photoresist, dielectric layer, buffer layer, diffusion barrier layer, etc., used during the fabrication and / or patterning of the metal-containing film 20. For example, the polymer residue is a polymer containing carbon, silicon, fluorine, or any combination thereof.

[0120] The metal-containing residue is any residue containing metal that is separated from the metal-containing film during the production and / or patterning of the metal-containing film 20.

[0121] Referring to Figure 1, a method for manufacturing an electronic element according to one embodiment includes the steps of: preparing a substrate provided with a metal-containing film (S100); bringing the metal-containing film into contact with the composition (S110); and carrying out subsequent steps to manufacture an electronic element (S120).

[0122] According to one embodiment, the electronic element is a semiconductor element.

[0123] For example, the steps of preparing a substrate to which the metal-containing film is provided (S100) and bringing the metal-containing film into contact with the composition (S110) can be used in the trench and via hole pattern formation steps for forming bit line electrodes in a semiconductor device manufacturing method.

[0124] Hereinafter, with reference to Figures 4A to 4J, an embodiment of the trench and via hole pattern formation process for forming bit line electrodes using the above composition will be described.

[0125] Figure 4A shows a portion of a semiconductor substrate (transistors and the like are not shown) including a first dielectric layer 103 and a metal layer 101. The metal layer 101 includes, for example, at least one of copper and cobalt. A first diffusion barrier layer 105 is disposed between the first dielectric layer 103 and the metal layer 101. The first diffusion barrier layer 105 includes, for example, tantalum, titanium, tungsten, tantalum nitride, titanium nitride, tungsten nitride, or any combination thereof.

[0126] A second diffusion barrier layer 107 is placed on the first dielectric layer 103 and the metal layer 101 in Figure 4A. The second diffusion barrier layer 107 includes, for example, silicon nitride nitrogen-doped silicon carbide or aluminum oxide.

[0127] A second dielectric layer 109 is placed on the second diffusion barrier layer 107 in Figure 4A. The second dielectric layer 109 includes, for example, an ULK (ultra-low K) dielectric or a silicon oxide.

[0128] On the second dielectric layer 109 in Figure 4A, a mechanically robust buffer layer 111 is placed to prevent damage to the second dielectric layer 109 during the deposition of the hard mask layer 113. The buffer layer 111 includes, for example, tetraethyl orthosilicate (TEOS) or carbon-doped silicon oxide (SiCOH).

[0129] A hard mask layer 113 is placed on the buffer layer 111 in Figure 4A. The hard mask layer 113 comprises i) titanium nitride (TiN), ii) titanium nitride (e.g., TiAlN) further comprising indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof. For example, the hard mask layer 113 comprises titanium nitride.

[0130] A first photoresist 115 is placed on the hard mask layer 113 in Figure 4A.

[0131] Next, the first photoresist 115 is patterned to form a pattern of the first photoresist 115 having a first opening with a width t as shown in Figure 4B. Then, the hard mask layer 113 is etched by the pattern of the first photoresist 115 to open a portion of the buffer layer 111 as shown in Figure 4C. After that, for example, using ashing, the pattern of the first photoresist 115 is removed as shown in Figure 4D to form a pattern of the exposed hard mask layer 113.

[0132] Next, as shown in Figure 4E, a filler layer 117 is formed to cover the pattern of the hard mask layer 113, filling the openings in the pattern of the hard mask layer 113. The filler layer 117 includes, for example, hydrogen silsesquioxane (HSQ) or methylsilsesquioxane (MSQ).

[0133] Next, as shown in Figure 4F, a second photoresist 119 is formed on top of the filler layer 117, and then the second photoresist 119 is patterned to form a pattern of the second photoresist 119 having a second opening with width v, as shown in Figure 4G. Then, for example, using RIE (Reactive Ion Etching), the filler layer 117, a portion of the pattern of the hard mask layer 113, a portion of the buffer layer 111, and a portion of the second dielectric layer 109 located below the pattern of the second photoresist 119 are etched to partially form via holes, as shown in Figure 4H, and then the pattern of the second photoresist 119 and the filler layer 117 are removed.

[0134] Next, as shown in Figure 4I, the buffer layer 111, the second dielectric layer 109, and the second diffusion barrier layer 107 are etched using, for example, a dry etching process, according to the pattern of the hard mask layer 113, until the via holes reach the metal layer 101, thereby forming trenches and via hole patterns. The etching gas used in the dry etching process is, for example, carbon fluoride gas (e.g., CHF3, C2F6, CF4, C4F8, C2HF5, etc.).

[0135] As a result of the dry etching described above, as shown in Figure 4I, a large amount of residue R may be present on the inner walls of the trench and via hole patterns. The residue R includes etching gas residue, polymer residue, metal-containing residue, or any combination thereof. The etching gas residue includes reaction products with the etching gas itself and / or any substance that came into contact with the etching gas during the etching process using the etching gas (e.g., substances contained in the buffer layer 111, the second dielectric layer 109, etc.). The polymer residue is a polymer derived from various organic substances contained in the second photoresist 119, the second dielectric layer 109, the buffer layer 111, the second diffusion barrier layer 107, etc. For example, the polymer residue is a polymer containing carbon, silicon, fluorine, or any combination thereof. The metal-containing residue is, for example, a residue containing metals contained in the pattern of the hard mask layer 113.

[0136] The residue R in Figure 4I needs to be removed because it increases the electrical resistance of the semiconductor device or causes an electrical short circuit in the bit line electrodes that are formed later. On the other hand, for process simplification, the residue R and the pattern of the hard mask layer 113 need to be removed simultaneously. Furthermore, the metal layer 101 should not be substantially damaged when removing the residue R and the pattern of the hard mask layer 113.

[0137] To this end, by bringing a composition containing the aforementioned oxidizing agent, ammonium-based buffer, and etching modifier into contact with the substrate of Figure 4I, which includes a hard mask layer 113 pattern and a metal-containing film including the metal layer 101, the substrate of Figure 4J can be fabricated in which i) residue R generated on the inner walls of the trench and via hole patterns is removed, ii) the pattern of the hard mask layer 113 is removed, and iii) the metal layer 101 is not substantially damaged. Although not limited by any particular theory, for example, the pattern of the hard mask layer 113 is removed by the oxidizing agent and ammonium-based buffer, and the residue R is removed by the etching modifier, while at the same time, the metal layer 101 is not substantially etched. Then, by filling the trench and via hole patterns of Figure 4J with a metallic substance, bit line electrodes and the like can be formed.

[0138] Examples 1 and 2 and Comparative Examples R1 to R4 Compositions for Examples 1 and 2 and Comparative Examples R1 to R4 were prepared by weighing 25 wt% hydrogen peroxide, 0.5 wt% (NH4)2HPO4, 0.5 wt% tetramethylammonium hydroxide (TMAH), and 0.1 wt% ethylenediaminetetraacetic acid (EDTA) with the substances listed in Table 1 as etching modifiers, and then mixing them to produce the compositions for Examples 1 and 2 and Comparative Examples R1 to R4. The remainder of each composition is water (deionized water).

[0139] Comparative Example R5 A composition for Comparative Example R5 was prepared by mixing 25 wt% hydrogen peroxide, 0.5 wt% (NH4)2HPO4, 0.5 wt% TMAH, and 0.1 wt% EDTA. The remainder of the composition is water (deionized water).

[0140] Evaluation Example 1 The pH of the composition of Example 1 was evaluated using a pH meter, and bubble formation and phase separation were visually evaluated in the composition. The results are summarized in Table 1.

[0141] Next, a substrate containing the composition of Example 1 (25°C) was immersed in a dip-type bath containing trenches and via hole patterns for forming bit line electrodes, with residue present on the inner walls of the trenches and via hole patterns. After immersion for 5 minutes, a rinsing and drying process was carried out, and the removal of residue was evaluated by AFM (Atomic Force Microscopy) topography analysis, and the results are summarized in Table 1. The substrate is a substrate with trenches and via hole patterns formed as shown in Figure 4I. Of the substrate, the metal layer 101 contains copper, the second dielectric layer 109 contains silicon oxide, the hard mask layer 113 contains titanium nitride, the buffer layer 111 contains carbon-doped silicon oxide, the second diffusion barrier layer 107 contains aluminum oxide, and the etching gas used in the dry etching process was CF4.

[0142] The above tests were repeated using each of the compositions from Example 2 and Comparative Examples R1 to R5, and the results are summarized in Table 1.

[0143] [Table 1]

[0144] Bubble formation "N": No bubbles are observed in the composition. Bubble formation "Y": Bubbles are observed in the composition. Phase separation "N": No phase separation is observed in the composition. Phase separation "Y": Phase separation is observed in the composition. Good: No residue longer than 10 nm was observed. Defective: Residues longer than 10 nm are observed. [ka]

[0145] Table 1 confirms that the compositions of Examples 1 and 2 have superior residue removal capabilities compared to the compositions of Comparative Examples R1 to R5. Furthermore, unlike the compositions of Comparative Examples R2 and R3, the compositions of Examples 1 and 2 do not exhibit bubble formation or phase separation, confirming their superior stability.

[0146] Evaluation Example 2 The composition of Example 1 was placed in two separate beakers and heated to 50°C. The plasma-etched copper film and titanium nitride film were then immersed in the respective beakers for 10 minutes and 0.5 minutes, respectively. The thickness of the copper film was measured using XRF (X-Ray Fluorescence Spectrometry) (S8 Tiger, BRUKER), and the thickness of the titanium nitride film was measured using an ellipsometer (M-2000, JAWoolam). The etching rates (Å / min) for the copper film and the titanium nitride film of the composition of Example 1 were evaluated. The etching rate for the titanium nitride film was divided by the etching rate for the copper film to evaluate R (TiN / Cu), and the results were summarized in Table 2.

[0147] The above tests were repeated using the compositions of Example 2, Comparative Example R1, and Comparative Example R5, and the results are summarized in Table 2.

[0148] [Table 2]

[0149] Table 2 confirms that the compositions of Examples 1 and 2 exhibit improved copper film etching suppression ability and improved etching selectivity of the titanium nitride film relative to the copper film compared to the compositions of Comparative Examples R1 and R5.

[0150] Evaluation Example 3 The composition of Example 1 was placed in two separate beakers and heated to 50°C. The plasma-etched cobalt film and titanium nitride film were then immersed in the respective beakers for 5 minutes and 0.5 minutes, respectively. The thickness of the cobalt film was measured using an XRF (S8 Tiger, BRUKER), and the thickness of the titanium nitride film was measured using an ellipsometer (M-2000, JAWoolam). The etching rates (Å / min) for the cobalt film and the titanium nitride film of the composition of Example 1 were evaluated. The etching rate for the titanium nitride film was divided by the etching rate for the cobalt film to evaluate R (TiN / Co), and the results were summarized in Table 3.

[0151] The above tests were repeated using the compositions of Example 2, Comparative Example R4, and Comparative Example R5, and the results are summarized in Table 3.

[0152] [Table 3]

[0153] Table 3 shows that the compositions of Examples 1 and 2 exhibit improved cobalt film etching suppression ability and improved etching selectivity of the titanium nitride film relative to the cobalt film compared to the compositions of Comparative Examples R4 and R5.

[0154] Comparative Examples R11-R13 Compositions R11 to R13 were prepared by weighing 25 wt% hydrogen peroxide, 0.5 wt% (NH4)2HPO4, 0.5 wt% TMAH, and 0.1 wt% EDTA, along with the substances listed in Table 4 as etching modifiers, according to the measurements in Table 4, and then mixing them. The remainder of each composition was water (deionized water).

[0155] Evaluation Example 4 The pH, etching rate (Å / min) for the copper film, etching rate (Å / min) for the cobalt film, etching rate (Å / min) for the titanium nitride film, and R(TiN / Cu) and R(TiN / Co) for Comparative Examples R11 to R13 were evaluated using the same method as described in Evaluation Examples 2 and 3. The results were then summarized in Table 4 along with the data from Examples 1 and 2.

[0156] [Table 4] [ka]

[0157] Table 4 shows that the compositions of Examples 1 and 2 exhibit improved copper film etching suppression ability, etching selectivity ratio of the titanium nitride film to the copper film, cobalt film etching suppression ability, and etching selectivity ratio of the titanium nitride film to the cobalt film compared to the compositions of Comparative Examples R11 to R13.

Claims

1. It comprises an oxidizing agent, an ammonium-based buffer, and an etching controller. The etching modifier comprises a compound represented by chemical formula 1, comprising: 【Chemistry 1】 In the aforementioned chemical formula 1, R １ C １ -C ３０ Alkyl or C ２ -C ３０ It is an alkenyl group, R ２ to R ７ are, independently of each other, hydrogen, C １ -C ３０ alkyl group, or C ２ -C ３０ alkenyl group, and L １ and L ２ They are independent of each other, C １ -C ３０ Alkylene group or C ２ -C ３０ It is an alkenylene group, X and Z are independently hydrogen, alkali metal, or ammonium group. The aforementioned R １ ~R ７ At least one of the methylene groups contained therein is optionally substituted with O or S. The aforementioned R １ ~R ７ , L １ and L ２ At least one of the hydrogen atoms contained in is selectively a halogen atom, a hydroxyl group, a thiol group, or C １ -C ３０ Alkoxy group, or C １ -C ３０ It is substituted with an alkylthio group.

2. The composition according to claim 1, wherein the oxidizing agent comprises hydrogen peroxide.

3. The composition according to claim 1, wherein the content of the oxidizing agent is 16 wt% to 50 wt% per 100 wt% of the composition.

4. The ammonium buffer is N(A) １１ ) (A １２ ) (A １３ ) (A １４ It contains an ammonium group represented by ), A １１ ~A １４ These are, independently of each other, hydrogen and C １ -C ３０ alkyl group, C ２ -C ３０ Alkenyl group, C ３ -C ３０ Carbon ring group, or C １ -C ３０ The composition according to claim 1, wherein the group is a heterocyclic group.

5. The composition according to claim 1, wherein the ammonium buffer comprises at least one of the following: hydroxide, acetate, bicarbonate, benzoate, carbonate, formate, nitrate, hydrogensulfate, carbamate, sulfamate, citrate, phosphate, sulfite, sulfobenzoate, oxalate, lactate, tartrate, dihydrogencitrate, glutamate, salicylate, bioxalate, octanoate, propionate, glycolate, and gluconate.

6. The composition according to claim 1, wherein the ammonium buffer comprises at least one of the compounds represented by chemical formula 11-1, chemical formula 11-2, chemical formula 11-3, and chemical formula 11-4: <Chemical formula 11-1> [N(A １１ )(A １２ )(A １３ )(A １４ )] ３ PO ４ <Chemical formula 11-2> [N(A １１ )(A １２ )(A １３ )(A １４ )] ２ KOO ４ <Chemical formula 11-3> [N(A １１ )(A １２ )(A １３ )(A １４ )]H ２ PO ４ <Chemical formula 11-4> [N(A １１ )(A １２ )(A １３ )(A １４ )]OH In the above chemical formulas 11-1 to 11-4, A １１ ~A １４ These are, independently of each other, hydrogen and C １ -C ３０ alkyl group, C ２ -C ３０ Alkenyl group, C ３ -C ３０ Carbon ring group, or C １ -C ３０ It is a heterocyclic group.

7. The composition according to claim 1, wherein the content of the ammonium buffer is 0.01 wt% to 10 wt% per 100 wt% of the composition.

8. In the above chemical formula 1, R １ C ５ -C ３０ Alkyl or C ５ -C ３０ The composition according to claim 1, wherein the group is an alkenyl group.

9. In the above chemical formula 1, R １ The composition according to claim 1, wherein the atoms contained are carbon and hydrogen.

10. In the above chemical formula 1, L １ and L ２ They are independent of each other, C １ -C ４ The composition according to claim 1, wherein the group is alkylene.

11. The composition according to claim 1, wherein the content of the etching modifier is 0.001 wt% to 10 wt% per 100 wt% of the composition.

12. The composition according to claim 1, having a pH in the range of 5.0 to 12.

0.

13. The steps include preparing a substrate to which a metal-containing film is provided, A method for treating a metal-containing film, comprising the step of bringing the metal-containing film into contact with the composition described in any one of claims 1 to 12.

14. The method for treating a metal-containing film according to claim 13, wherein the metal contained in the metal-containing film includes titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

15. The method for treating a metal-containing film according to claim 13, wherein the metal-containing film comprises a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.

16. The method for treating a metal-containing film according to claim 13, wherein a portion or more of the metal-containing film is etched or cleaned during the contact step between the metal-containing film and the composition.

17. The metal-containing film comprises a first region and a second region. The method for treating a metal-containing film according to claim 13, wherein the second etching rate at which the composition etches the second region is greater than the first etching rate at which the composition etches the first region.

18. The method for treating a metal-containing film according to claim 17, wherein the first region contains at least one of cobalt and copper, and the second region contains titanium nitride.

19. During the contact step between the metal-containing film and the composition, residues on the surface of the metal-containing film are removed, thereby cleaning a portion or more of the metal-containing film. The method for treating a metal-containing film according to claim 13, wherein the residue includes etching gas residue, polymer residue, metal-containing residue, or any combination thereof.

20. The steps include preparing a substrate to which a metal-containing film is provided, A step of bringing the metal-containing film into contact with the composition according to any one of claims 1 to 12, A method for manufacturing an electronic element, comprising the step of carrying out subsequent manufacturing processes to produce an electronic element.

Images