Compositions, methods of treating metal-containing films by using the compositions, and methods of manufacturing electronic devices by using the compositions

Abstract

The invention provides compositions, methods for treating metal-containing films using the compositions, and methods for manufacturing electronic devices using the compositions. The compositions may include oxidants, ammonium-based buffers, and etching control agents. The etching control agents may include compounds represented by Formula 1. A description of Formula 1 is provided in the specification.

Description

[0001] Cross-reference to related applications

[0002] This application is based on and claims priority to Korean Patent Application No. 10-2025-0007549, filed on January 17, 2025, with the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

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

[0004] To meet consumer demands for superior performance and low prices, increased integration and improved reliability of electronic devices, such as semiconductor devices, are advantageous. As the integration of semiconductor devices increases, damage to components during the manufacturing process can more significantly impact the reliability and / or electrical characteristics of the semiconductor device. In particular, various processing techniques, such as etching and cleaning, can be applied to films (e.g., metal-containing films) during semiconductor device manufacturing. Compositions with suitable etching rates and / or excellent cleaning capabilities are advantageous for more efficient processing of metal-containing films. Summary of the Invention

[0005] Provides compositions having improved etching selectivity and / or cleaning properties, methods for treating metal-containing films using said compositions, and / or methods for manufacturing electronic devices using said compositions.

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

[0007] According to embodiments of this disclosure, the composition (e.g., an etching composition) may include:

[0008] Oxidizing agents, ammonium-based buffers, and etching control agents,

[0009] The etching control agent may include a compound represented by Formula 1:

[0010] Formula 1

[0011] .

[0012] In Equation 1,

[0013] R1 can be C1-C 30 Alkyl or C2-C 30 alkenyl,

[0014] R2 to R7 can each be hydrogen, C1-C, or independently. 30 Alkyl, or C2-C 30 alkenyl,

[0015] L1 and L2 can each be independently C1-C 30 Alkylene or C2-C 30 alkenyl,

[0016] X and Z can each be independently hydrogen, alkali metal, or ammonium groups.

[0017] At least one methylene group included in one or more of R1 to R7 may optionally be replaced by O or S, and

[0018] At least one hydrogen atom included in one or more of R1 to R7, L1, and L2 may optionally be replaced by a halogen atom, hydroxyl group, thiol group, C1-C 30 alkoxy, or C1-C 30 Alkyl thio group substitution.

[0019] According to embodiments of this disclosure, a method for processing (e.g., etching) a metal-containing film may include:

[0020] Prepare a substrate on which a metal-containing film is deposited; and

[0021] The metal-containing film is brought into contact with the composition.

[0022] The metals included 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.

[0023] In some embodiments, at least a portion of the metal-containing film can be etched and / or cleaned by contacting the metal-containing film with the composition.

[0024] In some embodiments, the metal-containing film may have a first region and a second region, and

[0025] The second etching rate at which the composition etches the second region can be greater than the first etching rate at which the composition etches the first region.

[0026] In some embodiments, the first region may include Co, Cu, or a combination thereof, and the second region may include titanium nitride (titanium nitride).

[0027] In some embodiments, by contacting the metal-containing film with the composition, at least a portion of the metal-containing film can be cleaned by removing residues from its surface.

[0028] The residues may include etching gas residues, polymer residues, metal-containing residues, or any combination thereof.

[0029] According to embodiments of this disclosure, a method for manufacturing an electronic device (e.g., a semiconductor device) may include:

[0030] Prepare a substrate on which a metal-containing film is deposited.

[0031] The metal-containing film is brought into contact with the composition, and

[0032] The electronic device (e.g., the semiconductor device) is manufactured by performing one or more subsequent manufacturing processes.

[0033] It will be understood that the technical features described herein regarding the methods for processing metal-containing films are also applicable to the methods described herein for manufacturing electronic devices (e.g., semiconductor devices). Attached Figure Description

[0034] The above and other aspects, features, and advantages of some embodiments of this disclosure will become more apparent from the following description taken in conjunction with the accompanying drawings, wherein:

[0035] Figure 1 It is a process flow diagram illustrating the implementation of a method for manufacturing electronic devices;

[0036] Figure 2 and 3 Each of the above figures is a brief illustration of an implementation method for processing metal-containing films; and

[0037] Figures 4A to 4J Each is a cross-sectional view illustrating an implementation of a trench-via hole patterning process for bit line electrode formation. Detailed Implementation

[0038] The embodiments will now be described in detail, examples of which are shown in the accompanying drawings, wherein the same reference numerals always refer to the same elements. In this respect, the embodiments may take different forms and should not be construed as limited to the description set forth herein. Therefore, the embodiments are described below only by reference to the accompanying drawings to illustrate aspects. As used herein, the term “and / or” includes any and all combinations of one or more of the associated enumerated items. Expressions such as “at least one of…” modify the entire list of elements and not individual elements of the list when preceding or following it. For example, “at least one of A, B, and C” and similar language (e.g., “at least one of A, B, and C” and “at least one of A, B, or C”) can be interpreted as only A, only B, only C, or any combination of two or more of A, B, and C, such as ABC, AB, BC, and AC.

[0039] When the terms “about” or “substantially” are used in this specification to refer to numerical values, it is intended that the relevant numerical value includes manufacturing or operational tolerances (e.g., ±10%) around the stated value. Similarly, when the terms “generally” and “substantially” are used to refer to geometry, it is intended that precision of the geometry is not required, but tolerance for the shape is within the scope of this disclosure. Furthermore, regardless of whether a numerical value or shape is modified by “about” or “substantially,” it will be understood that these values ​​and shapes should be interpreted as including manufacturing or operational tolerances (e.g., ±10%) around the stated numerical value or shape. When a range is described in detail, the range includes all values ​​within that range, for example, in increments of 0.1%.

[0040] Metal-containing membranes

[0041] The metals included in the metal-containing film can be alkali metals (e.g., sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), etc.), alkaline earth metals (e.g., beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), etc.), lanthanides (e.g., lanthanum (La), europium (Eu), terbium (Tb), ytterbium (Yb), etc.), transition metals (e.g., scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (… In), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), nickel (Ni), copper (Cu), silver (Ag), zinc (Zn), etc.), later transition metals (e.g., aluminum (Al), gallium (Ga), indium (In), thallium (Tl), tin (Sn), bismuth (Bi), etc.), or any combination thereof.

[0042] In an embodiment, the metal included in the metal-containing film may include Ti, In, Al, Co, La, Sc, Ga, W, Mo, Ru, Zn, Hf, Cu, or any combination thereof.

[0043] In one or more embodiments, the metal-containing film may include two or more different types of metals.

[0044] In one or more embodiments, the metal included in the metal-containing film may include

[0045] i) Ti, and

[0046] ii) In, Al, Co, La, Sc, Ga, W, Mo, Ru, Zn, Hf, Cu, or any combination thereof.

[0047] In one or more embodiments, the metal-containing film may include Al, Ti, La, Co, Cu, or any combination thereof.

[0048] In one or more embodiments, the metal-containing film may include Ti.

[0049] In one or more embodiments, the metal-containing film may include Co.

[0050] In one or more embodiments, the metal-containing film may include Cu.

[0051] In one or more embodiments, the metal-containing film may include Ti and Co.

[0052] In one or more embodiments, the metal-containing film may include Ti and Cu.

[0053] The metal-containing film may include metal, metal nitride, metal oxide, metal oxynitride, or a combination thereof.

[0054] In an embodiment, the metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof, and the aforementioned metal, the metal included in the metal nitride, the metal included in the metal oxide, and the metal included in the metal oxynitride may each include Ti, In, Al, Co, La, Sc, Ga, W, Mo, Ru, Zn, Hf, Cu, or any combination thereof.

[0055] In one or more embodiments, the metal-containing film may include the metal nitride.

[0056] In one or more embodiments, the metal-containing film may include the aforementioned metal (e.g., Co, Cu, or a combination thereof).

[0057] In one or more embodiments, the metal-containing film may include a metal nitride and a metal (e.g., Co, Cu, or a combination thereof). For example, the metal included in the metal nitride may be different from the metal itself.

[0058] In one or more embodiments, the metal-containing film may include a metal nitride and a metal (e.g., Co, Cu, or a combination thereof), and the metal included in the metal nitride may include In, Ti, Al, La, Sc, Ga, Zn, Hf, or any combination thereof.

[0059] In one or more embodiments, the metal-containing film may include titanium nitride and metal (e.g., Co, Cu, or combinations thereof), and the titanium nitride may optionally further include In, Al, La, Sc, Ga, Hf, Zn, W, Si, or any combination thereof.

[0060] In one or more embodiments, the metal-containing film may include titanium nitride, titanium nitride comprising Al (e.g., titanium aluminum nitride or TiAlN), titanium nitride comprising La, etc.

[0061] In one or more embodiments, the metal-containing film may include a metal oxide. The metal included in the metal oxide may include Ti, Al, La, Sc, Ga, Hf, or any combination thereof. In embodiments, the metal-containing film may include aluminum oxide (e.g., Al₂O₃), indium gallium zinc oxide (IGZO), etc.

[0062] In one or more embodiments, the metal-containing film may include the metal nitride and the metal oxide.

[0063] In one or more embodiments, in addition to the metal, the metal-containing film may further include quasi-metals (e.g., boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), etc.), non-metals (e.g., nitrogen (N), phosphorus (P), oxygen (O), sulfur (S), selenium (Se), etc.), or any combination thereof.

[0064] For example, the metal-containing film may further comprise silicon oxide.

[0065] In one embodiment, the metal-containing film may include

[0066] a) i) titanium nitrides, or ii) titanium nitrides further comprising In, Al, La, Sc, Ga, Hf, Zn, W, Si, or any combination thereof, and

[0067] b) Co, Cu, or combinations thereof.

[0068] The metal-containing membrane may have a single-layer structure composed of one or more materials or a multi-layer structure comprising different materials. Multiple membranes included in the multi-layer structure may be stacked vertically or arranged horizontally. The single-layer structure and the multi-layer structure may have various three-dimensional patterns (e.g., through-holes, trenches, etc.).

[0069] In one embodiment, the metal-containing film may have a first region and a second region, and the composition etches the second region at a second etching rate that is greater than the composition etches the first region at a first etching rate. During a processing of the metal-containing film (e.g., an etching process, a cleaning process, etc.), at least a portion of the first region and at least a portion of the second region may come into contact with the composition, and because the second etching rate is greater than the first etching rate, the second region may be etched faster than the first region. The first region and the second region may be spaced apart from each other.

[0070] For example, the first region may include a metal, a metal oxide (e.g., aluminum oxide), silicon oxide, or a combination thereof.

[0071] In an implementation, the first region may include Co, Cu, or a combination thereof.

[0072] In one or more embodiments, the second region may include a metal nitride (e.g., a titanium nitride).

[0073] In one or more embodiments, the second region may include i) a titanium nitride, ii) a titanium nitride (e.g., TiAlN) further comprising In, Al, La, Sc, Ga, Zn, Hf, or any combination thereof, or iii) a combination thereof.

[0074] In one or more embodiments, the first region and the second region may each include i) a titanium nitride, ii) a titanium nitride comprising In, Al, La, Sc, Ga, Zn, Hf, or any combination thereof, or iii) a combination thereof.

[0075] In one or more embodiments, the first region may include Co, Cu, or a combination thereof, while the second region may not include Co and Cu.

[0076] In one or more embodiments, the first region may include Co, Cu, or a combination thereof, and the second region may include i) a titanium nitride, ii) a titanium nitride (e.g., TiAlN) further including In, Al, La, Sc, Ga, Zn, Hf, or any combination thereof, or iii) a combination thereof.

[0077] In one or more embodiments, the first region may include Co, Cu, or a combination thereof, and the second region may include titanium nitride, titanium nitride further including Al (e.g., TiAlN), or any combination thereof.

[0078] In one or more embodiments, the first region may include a Co film, a Cu film, or a combination thereof, and the second region may include a titanium nitride film, a titanium nitride film further comprising Al (e.g., a titanium aluminum nitride film or a TiAlN film), or any combination thereof.

[0079] In one or more embodiments, the first region may include a Co film, a Cu film, or a combination thereof, and the second region may include a titanium nitride film or a titanium nitride film further comprising Al (e.g., a titanium aluminum nitride film or a TiAlN film).

[0080] The etched film described herein may refer to the removal of at least some of the material constituting the film to be etched.

[0081] Composition

[0082] The composition may include an oxidant, an ammonium-based buffer, and an etching control agent.

[0083] The composition can be used in various processing techniques for the metal-containing film, such as etching, cleaning, polishing, etc.

[0084] The composition may further comprise water. The composition may further comprise a chelating agent (e.g., ethylenediaminetetraacetic acid (EDTA)).

[0085] Oxidizing agent

[0086] The oxidant can be used to etch at least a portion of the metal-containing film by oxidizing at least some of the metals included in the metal-containing film and forming a water-soluble complex, and may include, for example, at least one of hydrogen peroxide, nitric acid, and ammonium sulfate.

[0087] In some embodiments, the oxidant may include hydrogen peroxide.

[0088] In one or more embodiments, the oxidant is hydrogen peroxide.

[0089] The amount (by weight) of the oxidant may be, for example, within the following ranges for 100% of the composition: about 16% to about 50% by weight, about 18% to about 50% by weight, about 20% to about 50% by weight, about 22% to about 50% by weight, about 25% to about 50% by weight, about 16% to about 45% by weight, about 18% to about 45% by weight, about 20% to about 45% by weight, about 22% to about 45% by weight, about 25% to about 45% by weight, about 16% to about 40% by weight, about 18% to about 40% by weight, about 20% to about 40% by weight, about 22% to about 40% by weight. 0% by weight, about 25% by weight to about 40% by weight, about 16% by weight to about 35% by weight, about 18% by weight to about 35% by weight, about 20% by weight to about 35% by weight, about 22% by weight to about 35% by weight, about 25% by weight to about 35% by weight, about 16% by weight to about 30% by weight, about 18% by weight to about 30% by weight, about 20% by weight to about 30% by weight, about 22% by weight to about 30% by weight, about 25% by weight to about 30% by weight, about 16% by weight to about 27% by weight, about 18% by weight to about 27% by weight, about 20% by weight to about 27% by weight, about 22% by weight to about 27% by weight, or about 25% by weight to about 27% by weight.

[0090] When the amount of the oxidant is within the above range, the composition can simultaneously exhibit both excellent etching selectivity and excellent cleaning performance.

[0091] Ammonium-based buffers

[0092] The ammonium-based buffer can be used to maintain a high concentration of anions generated by the oxidant and to stabilize water-soluble complexes formed when the anions oxidize at least a portion of the metal contained in the metal-containing film. By using such an ammonium-based buffer, at least a portion of the metal-containing film can be effectively etched.

[0093] The ammonium-based buffer may include an ammonium group.

[0094] In an embodiment, the ammonium-based buffer may include N(A) 11 (A) 12 (A) 13 (A) 14 The ammonium group represented by ) is where A 11 To A 14 Each can be independently hydrogen, C1-C 30 Alkyl, C2-C 30 alkenyl, C3-C 30 Carbocyclic groups, or C1-C 30 Heterocyclic groups.

[0095] For example, A 11 To A 14 Each can be independently hydrogen or C1-C 10 alkyl.

[0096] In one or more embodiments, the ammonium-based buffer may include at least one of hydroxides, acetates, bicarbonates, benzoates, carbonates, formates, nitrates, bisulfates, carbamates, aminosulfonates, citrates, phosphates, sulfites, sulfobenzoates, oxalates, lactates, tartrates, dihydrogen citrate, glutamate, salicylates, bioxalate, octanoate, propionate, glycolate, or gluconate.

[0097] In one or more embodiments, the ammonium-based buffer may include a phosphate or a hydroxide. A phosphate as an ammonium-based buffer refers to an ammonium-based compound containing phosphate ions.

[0098] In one or more embodiments, the ammonium-based buffer may include ammonium-based compounds containing phosphate (e.g., compounds represented by Formula 11-1, Formula 11-2, Formula 11-3, or any combination thereof), ammonium-based compounds containing hydroxide (e.g., compounds represented by Formula 11-4), or combinations thereof.

[0099] In one or more embodiments, the ammonium-based buffer may include an ammonium-based compound containing phosphate.

[0100] In one or more embodiments, the ammonium-based buffer may include a compound represented by Formula 11-1, a compound represented by Formula 11-2, a compound represented by Formula 11-3, a compound represented by Formula 11-4, or any combination thereof:

[0101] Formula 11-1

[0102] [N(A 11 (A) 12 (A) 13 (A) 14 )]3PO4

[0103] Formula 11-2

[0104] [N(A 11 (A) 12 (A) 13 (A) 14 )]2HPO4

[0105] Formula 11-3

[0106] [N(A 11(A) 12 (A) 13 (A) 14 H2PO4

[0107] Formula 11-4

[0108] [N(A 11 (A) 12 (A) 13 (A) 14 )]OH

[0109] The descriptions of equations 11-1 to 11-4 can each be as defined in this document.

[0110] In one or more embodiments, the ammonium-based buffer may include ammonium phosphate ((NH4)3PO4), diammonium monohydrogen phosphate ((NH4)2HPO4), ammonium dihydrogen phosphate ((NH4)H2PO4), tris(tetramethylammonium phosphate)([N(CH3)4]3PO4), di(tetramethylammonium monohydrogen phosphate)([N(CH3)4]2HPO4), tetramethylammonium dihydrogen phosphate ([N(CH3)4]H2PO4), ammonium hydroxide, tetramethylammonium hydroxide (TMAH), or any combination thereof.

[0111] The amount (by weight) of the ammonium-based buffer may be, for example, within the following ranges based on 100% by weight of the composition: about 0.01% by weight to about 10% by weight, about 0.05% by weight to about 10% by weight, about 0.1% by weight to about 10% by weight, about 0.3% by weight to about 10% by weight, about 0.5% by weight to about 10% by weight, about 0.01% by weight to about 7% by weight, about 0.05% by weight to about 7% by weight, about 0.1% by weight to about 7% by weight, about 0.3% by weight to about 7% by weight, about 0.5% by weight to about 7% by weight, about 0.01% by weight to about 4% by weight. Amount%, about 0.05 wt% to about 4 wt%, about 0.1 wt% to about 4 wt%, about 0.3 wt% to about 4 wt%, about 0.5 wt% to about 4 wt%, about 0.01 wt% to about 2 wt%, about 0.05 wt% to about 2 wt%, about 0.1 wt% to about 2 wt%, about 0.3 wt% to about 2 wt%, about 0.5 wt% to about 2 wt%, about 0.01 wt% to about 1 wt%, about 0.05 wt% to about 1 wt%, about 0.1 wt% to about 1 wt%, about 0.3 wt% to about 1 wt%, or about 0.5 wt% to about 1 wt%.

[0112] In embodiments, the ammonium-based buffer may include ammonium-based compounds containing phosphate, ammonium-based compounds containing hydroxide, or combinations thereof, and the amounts (by weight) of the ammonium-based compounds containing phosphate and the ammonium-based compounds containing hydroxide may each be independently, for example, within the following ranges for 100% by weight of the composition: about 0.01% to about 10% by weight, about 0.05% to about 10% by weight, about 0.1% to about 10% by weight, about 0.3% to about 10% by weight, about 0.5% to about 10% by weight, about 0.01% to about 7% by weight, about 0.05% to about 7% by weight, about 0.1% to about 7% by weight, about 0.3% to about 7% by weight, about 0.5% to about 7% by weight, about 0.01% to about 4% by weight, about 0.05% to about 7% by weight. From about 4 wt%, about 0.1 wt% to about 4 wt%, about 0.3 wt% to about 4 wt%, about 0.5 wt% to about 4 wt%, about 0.01 wt% to about 2 wt%, about 0.05 wt% to about 2 wt%, about 0.1 wt% to about 2 wt%, about 0.3 wt% to about 2 wt%, about 0.5 wt% to about 2 wt%, about 0.01 wt% to about 1 wt%, about 0.05 wt% to about 1 wt%, about 0.1 wt% to about 1 wt%, about 0.3 wt% to about 1 wt%, about 0.5 wt% to about 1 wt%, about 0.01 wt% to about 0.7 wt%, about 0.05 wt% to about 0.7 wt%, about 0.1 wt% to about 0.7 wt%, about 0.3 wt% to about 0.7 wt%, about 0.5 wt% to about 0.7 wt%, or about 0.3 wt% to about 0.5 wt%.

[0113] When the amount of the ammonium-based buffer is within the above range, the composition can simultaneously have both improved (and / or superior) etch selectivity and improved (and / or superior) cleaning performance.

[0114] Etching control agent

[0115] The etching control agent can be used to control the etching rate, etc., by interacting with various metal atoms included in the metal-containing film, which is the target film to be treated. Furthermore, the etching control agent can be used to remove residues generated during the deposition process and / or patterning process of the metal-containing film.

[0116] The etching control agent may include a compound represented by Formula 1:

[0117] Formula 1

[0118] .

[0119] In Equation 1,

[0120] R1 can be C1-C 30 Alkyl or C2-C 30 alkenyl,

[0121] R2 to R7 are each independently hydrogen, C1-C 30 Alkyl, or C2-C 30 alkenyl,

[0122] L1 and L2 can each be independently C1-C 30 Alkylene or C2-C 30 alkenyl,

[0123] X and Z can each be independently hydrogen, alkali metal, or ammonium groups.

[0124] At least one methylene group included in R1 to R7 may optionally be replaced by O or S, and

[0125] At least one hydrogen atom included in R1 to R7, L1, and L2 may optionally be replaced by a halogen atom, hydroxyl group, thiol group, C1-C2 group, or C2-C2 group. 30 alkoxy, or C1-C 30 Alkyl thio group substitution.

[0126] In aqueous solution, the two groups in Formula 1, each represented by *-C(=O)O-, can strongly bond to the metal M (e.g., Co, Cu, etc.) included in the metal-containing film 2 (see the two “2a” in Formula 1'), such that the compound represented by Formula 1 can be effectively immobilized on the surface of the metal-containing film 2. Furthermore, the monoamine-based moiety comprising R1 to R7, L1, and L2 as defined above (see “2b” in Formula 1') can have a relatively large structure because all three N-bonded groups included in this moiety have “two or more carbon atoms”. Therefore, the compound represented by Formula 1 can provide a protective film with excellent surface properties on the surface of the metal-containing film 2 because intermolecular interactions are substantially suppressed by the compound represented by Formula 1. Thus, by using a composition comprising a compound represented by Formula 1, the etching rate can optionally be adjusted according to the metal included in the metal-containing film, and simultaneously, residues generated during the deposition and / or patterning processes of the metal-containing film can be removed more effectively.

[0127] Formula 1'

[0128]

[0129] Furthermore, the compound represented by Formula 1 dissolves substantially uniformly in the composition while substantially not forming micelles, thereby substantially limiting and / or preventing bubble formation and phase separation when preparing the composition and / or treating the metal-containing membrane using the composition. Bubble formation and phase separation in the composition can lead to reduced efficiency and stability of the processing of the metal-containing membrane, damage to the wafer, regeneration of residues, contamination of various equipment, etc., and therefore limiting and / or preventing bubble formation and phase separation during the preparation of the composition or during the treatment of the metal-containing membrane using the composition is advantageous. Although not particularly limited to a specific theory, compositions in which bubble formation and phase separation are observed during preparation and / or immediately after preparation can thus interfere with uniform contact between the metal-containing membrane and other active ingredients included in the composition and generate additional residues on the surface of the metal-containing membrane, and therefore compositions in which bubble formation and phase separation are observed may be substantially unsuitable for use in the treatment of the metal-containing membrane. Therefore, by using a composition comprising a compound represented by Formula 1, the etching rate can be optionally adjusted depending on the metal included in the metal-containing film without causing bubble formation and phase separation, and at the same time, residues generated during the deposition process and / or patterning process of the metal-containing film can be removed more effectively.

[0130] In the implementation method, R1 in Equation 1 can be:

[0131] 1) C3-C 30 Alkyl or C3-C 30 alkenyl,

[0132] 2) C5-C 30 Alkyl or C5-C 30 alkenyl,

[0133] 3) C7-C 30 Alkyl or C7-C 30 alkenyl,

[0134] 4) C3-C 20 Alkyl or C3-C 20 alkenyl,

[0135] 5) C5-C 20 Alkyl or C5-C 20 alkenyl,

[0136] 6) C7-C 20 Alkyl or C7-C 20 alkenyl,

[0137] 7) C3-C 11 Alkyl or C3-C 11 alkenyl,

[0138] 8) C5-C 11 Alkyl or C5-C 11 alkenyl, or

[0139] 9) C7-C 11 Alkyl or C7-C 11 Alkenyl group.

[0140] In one or more embodiments, the atoms included in R1 of Formula 1 may be carbon and hydrogen. When the atoms included in R1 of Formula 1 include carbon and hydrogen (e.g., when R1 is unsubstituted C1-C...), 30 Alkyl or unsubstituted C2-C 30 When alkenyl), the protective film provided on the surface of the metal-containing membrane 2 may have improved hydrophobicity due to the compound represented by Formula 1, thereby limiting and / or substantially preventing side reactions (e.g., surface oxidation of the metal-containing membrane) of the metal-containing membrane in contact with the composition.

[0141] In one or more embodiments, R2 to R7 in Formula 1 can each be independently...

[0142] i) Hydrogen, C1-C 20 Alkyl, or C2-C 20 alkenyl,

[0143] ii) Hydrogen, C1-C 10 Alkyl, or C2-C 10 alkenyl,

[0144] iii) Hydrogen, C1-C5 alkyl, or C2-C5 alkenyl,

[0145] iv) Hydrogen or methyl, or

[0146] v) Hydrogen.

[0147] In one or more embodiments, L1 and L2 in Equation 1 can each be independently...

[0148] i) C1-C 10 Alkylene

[0149] ii) C1-C4 alkylene groups,

[0150] iii) C1-C2 alkylene, or

[0151] iv) C1 alkylene (methylene).

[0152] In one or more embodiments, the atoms included in L1 and L2 of Formula 1 may be carbon and hydrogen. When the atoms included in L1 and L2 of Formula 1 are carbon and hydrogen (e.g., L1 and L2 are each unsubstituted C1-C...),30 Alkylene or unsubstituted C2-C 30 When the compound is (alkenyl), the protective film provided on the surface of the metal-containing membrane 2 may have improved hydrophobicity due to the compound represented by Formula 1, thereby limiting and / or substantially preventing side reactions (e.g., surface oxidation of the metal-containing membrane) of the metal-containing membrane in contact with the composition.

[0153] In one or more embodiments, X and Z in Formula 1 can each independently be hydrogen, Na, K, or N(A1)(A2)(A3)(A4), wherein A1 to A4 can each independently be hydrogen, C1-C 30 Alkyl, C2-C 30 alkenyl, C3-C 30 Carbocyclic groups, or C1-C 30 Heterocyclic groups. For example, A1 to A4 can each be independently hydrogen or C1-C. 10 alkyl.

[0154] In one or more embodiments, at least one methylene group (e.g., one or two methylene groups) included in R1 to R7 of Formula 1 may optionally be replaced by O or S.

[0155] In one or more embodiments, at least one hydrogen atom included in R1 to R7, L1, and L2 of Formula 1 may optionally be replaced by a halogen atom (e.g., -F, -Cl, -Br, etc.), a hydroxyl group, a thiol group, or a C1-C1 group. 30 Alkoxy groups (e.g., C1-C) 10 alkoxy), or C1-C 30 Alkyl thiols (e.g., C1-C) 10 Alkylthio group) is used as a substitute.

[0156] In one or more embodiments, the etching control agent may include at least one of compounds 1 and 2:

[0157] .

[0158] In one or more embodiments, the amount of the etching control agent may be, per 100% by weight of the composition, within the following ranges: about 0.001% by weight to about 10% by weight, about 0.01% by weight to about 10% by weight, about 0.1% by weight to about 10% by weight, about 0.2% by weight to about 10% by weight, about 0.001% by weight to about 5% by weight, about 0.01% by weight to about 5% by weight, about 0.1% by weight to about 5% by weight, about 0.2% by weight to about 5% by weight, about 0.00% by weight. 1 wt% to about 1 wt%, about 0.01 wt% to about 1 wt%, about 0.1 wt% to about 1 wt%, about 0.2 wt% to about 1 wt%, about 0.001 wt% to about 0.5 wt%, about 0.01 wt% to about 0.5 wt%, about 0.1 wt% to about 0.5 wt%, about 0.2 wt% to about 0.5 wt%, about 0.001 wt% to about 0.2 wt%, about 0.01 wt% to about 0.2 wt%, or about 0.1 wt% to about 0.2 wt%.

[0159] The pH of the composition can be in the range of about 1.0 to about 12.0, about 3.0 to about 12.0, about 5.0 to about 12.0, about 7.0 to about 12.0, about 1.0 to about 10.0, about 3.0 to about 10.0, about 5.0 to about 10.0, about 7.0 to about 10.0, about 3.0 to about 8.0, about 5.0 to about 8.0, or about 7.0 to about 8.0. When the pH of the composition is within the above range, the interaction between the etching control agent and the metal atoms included in the metal-containing film can be achieved more smoothly.

[0160] In one embodiment, the composition can be used in processes that process the metal-containing film, such as etching processes, cleaning processes, etc., of the metal-containing film. The metal-containing film is the same as that described elsewhere herein.

[0161] In embodiments, the composition can be used as a remover for etching byproducts, a remover for post-etching process byproducts, a remover for ashing process byproducts, a cleaning composition, a photoresist (PR) remover, an etching composition for packaging processes, a cleaning agent for packaging processes, a remover for adhesive substances on wafers, an etchant, a post-etching residue stripper, an ashing residue cleaner, a PR residue stripper, a post-CMP cleaner, etc.

[0162] Methods for processing metal-containing films and methods for manufacturing electronic devices

[0163] By using the aforementioned composition, the metal-containing film can be processed more effectively.

[0164] refer to Figure 1The method for processing a metal-containing film according to the embodiments may include: preparing a substrate on which a metal-containing film is disposed (S100); and contacting the metal-containing film with the composition (S110).

[0165] The metal-containing membrane is the same as that described elsewhere in this document.

[0166] For example, the metal included in the metal-containing film may include Ti, In, Al, Co, La, Sc, Ga, W, Mo, Ru, Zn, Hf, Cu, or any combination thereof.

[0167] In one or more embodiments, the metal-containing film may include metal, metal nitride, metal oxide, metal oxynitride, or any combination thereof.

[0168] In one or more embodiments, the metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof, and the aforementioned metal, the metal included in the metal nitride, the metal included in the metal oxide, and the metal included in the metal oxynitride may each include Ti, In, Al, Co, La, Sc, Ga, W, Mo, Ru, Zn, Hf, Cu, or any combination thereof.

[0169] In one or more embodiments, the metal-containing film may include titanium nitride.

[0170] In one or more embodiments, the metal-containing film may include Co, Cu, or a combination thereof.

[0171] In one embodiment, at least a portion of the metal-containing film can be etched and / or cleaned by contacting the metal-containing film with the composition.

[0172] In the composition, i) the oxidant can be used to etch at least a portion of the metal-containing film by oxidizing at least some of the metals included in the metal-containing film and forming a water-soluble complex; ii) the ammonium-based buffer can be used to maintain a high concentration of anions generated by the oxidant and to stabilize the water-soluble complex generated when the anions oxidize at least a portion of the metals included in the metal-containing film, thereby effectively etching at least a portion of the metal-containing film; iii) the compound represented by Formula 1 included in the etching control agent has two free *-C(=O)O atoms capable of strongly bonding with the metals (e.g., Co, Cu, etc.) included in the metal-containing film. -The groups represented, and the monoamine-based moieties including R1 to R7, L1, and L2 as defined above, which can substantially suppress intermolecular interactions, make it possible to provide a protective film with excellent surface properties and further improved hydrophobicity on the surface of the metal-containing film. Therefore, by using an etching control agent comprising a compound represented by Formula 1, the etching rate can be selectively adjusted depending on the metal included in the metal-containing film, and simultaneously, residues generated during the deposition and / or patterning processes of the metal-containing film can be effectively removed. Therefore, the aforementioned composition can be used in various processing techniques for the metal-containing film.

[0173] Figure 2 and 3 Each figure is a brief illustration of an implementation method for processing metal-containing films.

[0174] refer to Figure 2 A substrate 10 may be provided on which a metal-containing film 20 is disposed. An intermediate layer 11 may be disposed between the substrate 10 and the metal-containing film 20. Although not in Figure 2 As shown, however, circuit system elements (e.g., transistor gates, metal lines, impurity regions, semiconductor layers, etc.) may be arranged inside the substrate 10, on the substrate 10, and / or between the substrate 10 and the intermediate layer 11. In an embodiment, the metal-containing film 20 may be arranged directly on the substrate 10, and the intermediate layer 11 may be omitted.

[0175] The metal-containing film 20 may include a first region 21 and a second region 22. The first region 21 and the second region 22 may be spaced apart from each other, or at least a portion of the first region 21 and at least a portion of the second region 22 may be in direct contact with each other, and in this respect, the metal-containing film 20 may have various three-dimensional patterns. The second etching rate at which the composition etches the second region 22 may be greater than the first etching rate at which the composition etches the first region 21. For example, when the first etching rate is 0, the first region may not be etched.

[0176] refer to Figure 3 The composition can be used to etch a metal-containing film 20 such that at least a portion of the second region 22 can be etched to form a metal-containing film pattern 25. The etching process can be performed by contacting the composition with at least a portion of the first region 21 and at least a portion of the second region 22.

[0177] In one embodiment, the composition can be used to etch only at least a portion of the second region 22 without etching the first region 21. In one or more embodiments, the composition can be used to etch each of at least a portion of the first region 21 and at least a portion of the second region 22. Reference Figure 3The metal-containing film pattern 25 formed after etching may include at least a portion of the second region 22; however, if desired, an etching process may be performed to completely remove the second region 22 from the metal-containing film pattern 25. Various variations are possible in this regard.

[0178] In one or more embodiments, the first region 21 may include Co, Cu, or a combination thereof.

[0179] In one or more embodiments, the second region 22 may include a metal nitride (e.g., a titanium nitride).

[0180] In one or more embodiments, the second region 22 may include i) a titanium nitride, ii) a titanium nitride of In, Al, La, Sc, Ga, Zn, Hf, or any combination thereof (e.g., TiAlN), or iii) a combination thereof.

[0181] In one or more embodiments, the first region 21 and the second region 22 may each include i) a titanium nitride, ii) a titanium nitride comprising In, Al, La, Sc, Ga, Zn, Hf, or any combination thereof, or iii) a combination thereof.

[0182] In one or more embodiments, the first region 21 may include Co, Cu, or a combination thereof, while the second region 22 may not include Co and Cu.

[0183] In one or more embodiments, the first region 21 may include Co, Cu, or a combination thereof, and the second region 22 may include i) a titanium nitride, ii) a titanium nitride (e.g., TiAlN) further including In, Al, La, Sc, Ga, Zn, Hf, or any combination thereof, or iii) a combination thereof.

[0184] In one or more embodiments, the first region 21 may include Co, Cu, or a combination thereof, and the second region 22 may include titanium nitride, titanium nitride further including Al (e.g., TiAlN), or any combination thereof.

[0185] In one or more embodiments, the first region 21 may include a Co film, a Cu film, or a combination thereof, and the second region 22 may include a titanium nitride film, a titanium nitride film further including Al (e.g., a titanium aluminum nitride film or a TiAlN film), or any combination thereof.

[0186] In one or more embodiments, the first region 21 may be a Co film, and the second region 22 may be a titanium nitride film or a titanium nitride film further comprising Al (e.g., a TiAlN film).

[0187] In one or more embodiments, the first region 21 may be a Cu film, and the second region 22 may be a titanium nitride film or a titanium nitride film further comprising Al (e.g., a TiAlN film).

[0188] In one or more embodiments, by contacting the metal-containing film 20 with the composition, residues R on the surface of the metal-containing film 20 can be removed, thereby cleaning at least a portion of the metal-containing film 20. Therefore, as Figure 3 As shown, a metal-containing film pattern 25 without residue R can be formed.

[0189] Residue R is a byproduct generated during the deposition and / or patterning of the metal-containing film 20, and may be a substance remaining on the surface of the metal-containing film 20 and / or the surface of the metal-containing film pattern 25, thus causing an increase in resistance and / or an electrical short circuit between electrical wirings. Residue R may be etching residues generated due to etching, and may include, for example, etching gas residues, polymer residues, metal-containing residues, or any combination thereof.

[0190] The etching gas residue may originate from the etching gas used in dry etching. The etching gas may be, for example, a fluorocarbon gas. For example, the etching gas may include CHF3, C2F6, CF4, C4F8, C2HF5, etc. The etching gas residue may include the etching gas itself and / or reaction products from any substances that come into contact with the etching gas during the etching process using the etching gas.

[0191] The polymer residue may be a polymer derived from various organic substances included in photoresists, dielectric layers, buffer layers, diffusion barrier layers, etc., used during the fabrication and / or patterning of the metal-containing film 20. For example, the polymer residue may be a polymer comprising C, Si, F, or any combination thereof.

[0192] The metal-containing residue may be any residue of metal that was separated from the metal-containing membrane 20 during the manufacture and / or patterning of the metal-containing membrane 20.

[0193] refer to Figure 1 The method for manufacturing an electronic device according to the embodiments may include: preparing a substrate on which a metal-containing film is disposed (S100); contacting the metal-containing film with the composition (S110); and manufacturing the electronic device by performing one or more subsequent manufacturing processes (S120).

[0194] In this implementation, the electronic device may be a semiconductor device.

[0195] For example, preparing a substrate on which a metal-containing film is disposed (S100) and bringing the metal-containing film into contact with the composition (S110) can be used in a trench-via patterning process for forming bit line electrodes as part of a method for manufacturing electronic devices such as semiconductor devices.

[0196] In the following text, refer to Figures 4A to 4J This describes an embodiment of a trench-via patterning process for bit line electrode formation using the composition.

[0197] Figure 4A A portion of a semiconductor substrate (with transistors not shown) including a first dielectric layer 103 and a metal layer 101 is depicted. The metal layer 101 may include, for example, Co, Cu, or combinations thereof. A first diffusion barrier layer 105 may be disposed between the first dielectric layer 103 and the metal layer 101. The first diffusion barrier layer 105 may include, for example, Ta, Ti, W, tantalum nitride, titanium nitride, tungsten nitride, or any combination thereof.

[0198] The second diffusion barrier layer 107 can be arranged in... Figure 4A The first dielectric layer 103 and the metal layer 101 are located above the first dielectric layer 103 and the second diffusion barrier layer 107. The second diffusion barrier layer 107 may include, for example, silicon nitride, nitrogen-doped silicon carbide, or aluminum oxide.

[0199] The second dielectric layer 109 can be arranged in... Figure 4A The second diffusion barrier layer 107 is applied. The second dielectric layer 109 may include, for example, an ultra-low k (ULK) dielectric or silicon oxide.

[0200] exist Figure 4A On the second dielectric layer 109, a mechanically robust buffer layer 111 may be disposed to limit and / or prevent damage to the second dielectric layer 109 during the deposition of the hard mask layer 113. The buffer layer 111 may include, for example, tetraethyl orthosilicate (TEOS), carbon-doped silicon oxide (SiCOH), etc.

[0201] Hard mask layer 113 can be arranged in Figure 4A The buffer layer 111 is applied. The hard mask layer 113 may include i) titanium nitride, ii) further including titanium nitrides of In, Al, La, Sc, Ga, Zn, Hf, or any combination thereof (e.g., TiAlN), or iii) combinations thereof. For example, the hard mask layer 113 may include titanium nitride.

[0202] The first photoresist 115 can be applied to... Figure 4A On the hard mask layer 113.

[0203] Subsequently, by patterning the first photoresist 115, a pattern of the first photoresist 115 having a first opening with a width t can be formed, such as... Figure 4B As shown, and by etching the hard mask layer 113 according to the pattern of the first photoresist 115, the pattern of the hard mask layer 113 can be formed and a portion of the buffer layer 111 can be opened, as shown. Figure 4C As shown. For example, by ashing, the pattern of the first photoresist 115 can be removed to form the pattern of the exposed hard mask layer 113, as illustrated. Figure 4D As shown in the image.

[0204] Subsequently, as Figure 4E As shown, a filler layer 117 may be formed to cover the pattern of the hard mask layer 113, such that openings in the pattern of the mask layer 113 can be filled. The filler layer 117 may include, for example, hydrogen silsesquioxane (HSQ), methyl silsesquioxane (MSQ), etc.

[0205] Next, in such Figure 4F As shown, after the second photoresist 119 is formed on the filler layer 117, the second photoresist 119 can be patterned to form a pattern of the second photoresist 119 having a second opening with a width V, such as... Figure 4G As shown. For example, by reactive ion etching (RIE) or the like, a portion of the filler layer 117, a portion of the hard mask layer 113 pattern, a portion of the buffer layer 111, and a portion of the second dielectric layer 109 located beneath the pattern of the second photoresist 119 can be etched to partially form vias, such as... Figure 4H As shown in the diagram. Then, the pattern and filler layer 117 of the second photoresist 119 can be removed.

[0206] Next, as Figure 4I As shown, the buffer layer 111, the second dielectric layer 109, and the second diffusion barrier layer 107 can be etched according to the pattern of the hard mask layer 113 using, for example, a dry etching process, until the via reaches the metal layer 101, thereby forming a trench-via pattern. The etching gas used in the dry etching process can be, for example, a fluorocarbon gas (e.g., CHF3, C2F6, CF4, C4F8, C2HF5, etc.).

[0207] As a result of dry etching, a significant amount of residual R can exist on the inner walls of the trench-via pattern, such as... Figure 4IAs shown in the diagram. Residue R may include etching gas residues, polymer residues, metal-containing residues, or any combination thereof. Etching gas residues may include the etching gas itself and / or products resulting from the reaction with any substance (e.g., materials included in buffer layer 111, second dielectric layer 109, etc.) that comes into contact with the etching gas during an etching process using the etching gas. The polymer residues may include polymers derived from various organic materials included in the second photoresist 119, second dielectric layer 109, buffer layer 111, second diffusion barrier layer 107, etc. For example, the polymer residues may be polymers including C, Si, F, or any combination thereof. The metal-containing residues may include, for example, residues of metals included in the pattern of the hard mask layer 113.

[0208] Figure 4I The residue R shown can increase the resistance of the semiconductor device or cause an electrical short circuit in the bit line electrode to be formed later, and therefore removing the residue R is advantageous. Simultaneously, to simplify the process, it is advantageous to remove both the residue R and the pattern of the hard mask layer 113. Furthermore, in the removal of the residue R and the pattern of the hard mask layer 113, the metal layer 101 is essentially not removed.

[0209] For this purpose, when the composition comprising an oxidant, an ammonium-based buffer, and an etching control agent is combined with a metal-containing film comprising a patterned hard mask layer 113 and a metal layer 101, Figure 4I When in contact with the substrate, the following can be prepared: Figure 4J The substrate in which i) the residue R generated on the inner wall of the trench-via pattern can be removed, ii) the pattern of the hard mask layer 113 can be removed, and iii) the metal layer 101 is substantially undamaged. While not particularly limited to a specific theory, for example, the pattern of the hard mask layer 113 can be removed by an oxidant and an ammonium-based buffer, the residue R can be removed by an etching control agent, and simultaneously, the metal layer 101 can be substantially unetched. Afterwards, bit line electrodes, etc., can be formed by filling the trench-via pattern with a metallic material, etc.

[0210] Example

[0211] Examples 1 and 2 and Comparative Examples R1 to R4

[0212] 25% by weight of hydrogen peroxide, 0.5% by weight of (NH4)2HPO4, 0.5% by weight of tetramethylammonium hydroxide (TMAH), 0.1% by weight of ethylenediaminetetraacetic acid (EDTA), and the amounts of the compounds shown in Table 1 as etching control agents were weighed and mixed to prepare the compositions of Examples 1 and 2 and Comparative Examples R1 to R4. The remainder of each composition corresponds to water (deionized water).

[0213] Comparative Example R5

[0214] The composition of 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 corresponds to water (deionized water).

[0215] Evaluation of Example 1

[0216] Regarding the composition of Example 1, pH was evaluated using a pH meter, and the formation of bubbles or phase separation in the composition was visually assessed, with the results summarized in Table 1.

[0217] Next, a substrate having a trench-via pattern formed for the formation of bit line electrodes and containing residue on the inner wall of the trench-via pattern was immersed in a cleaning bath (immersion bath) (at 25°C) containing the composition of Example 1. After rinsing and drying the substrate, the removal of residue was evaluated by atomic force microscopy (AFM) morphology analysis, and the results are summarized in Table 1. The substrate is as follows... Figure 4I The substrate shown has a trench-via pattern, wherein the metal layer 101 comprises copper, the second dielectric layer 109 comprises silicon oxide, the hard mask layer 113 comprises titanium nitride, the buffer layer 111 comprises carbon-doped silicon oxide, the second diffusion barrier layer 107 comprises aluminum oxide, and the etching gas used in the dry etching process is CF4.

[0218] The same experiment was repeated using the compositions of Example 2 and Comparative Examples R1 to R5, and the results are summarized in Table 1.

[0219] Table 1

[0220]

[0221] Bubble formation "N": No bubble formation was observed in the composition.

[0222] Bubble formation "Y": Bubble formation was observed in the composition.

[0223] Phase separation “N”: No phase separation was observed in the composition.

[0224] Phase separation “Y”: Phase separation is observed in the composition.

[0225] Good: No residues with lengths of 10 nm or greater were observed.

[0226] Poor: Residues with lengths of 10 nm or greater were observed.

[0227]

[0228]

[0229]

[0230] Referring to Table 1, it is confirmed that the compositions of Examples 1 and 2 have improved and / or superior residue removal performance compared to the compositions of Comparative Examples R1 to R5. Furthermore, it is confirmed that, unlike the compositions of Comparative Examples R2 and R3, the compositions of Examples 1 and 2 have improved and / or superior stability, as no bubble formation and phase separation were observed.

[0231] Evaluation of Example 2

[0232] The composition of Example 1 was added to two beakers and heated to 50°C. A Cu film was then immersed in one beaker for 10 minutes, and a titanium nitride film was immersed in the other beaker for 0.5 minutes. The thickness of the Cu film was then measured using an X-ray fluorescence (XRF) spectrometer (S8 Tiger, BRUKER), and the thickness of the titanium nitride film was measured using an ellipsometry (M-2000, JAWoolam). The etching rates (Å / min) of the composition for the Cu film and the titanium nitride film were evaluated, and the etching rate for the titanium nitride film was divided by the etching rate for the Cu film to evaluate R(TiN / Cu). The results are summarized in Table 2.

[0233] The same experiment was repeated using the compositions of Example 2 and Comparative Examples R1 and R5, and the results are summarized in Table 2.

[0234] Table 2

[0235]

[0236] Referring to Table 2, it is confirmed that, compared with the compositions of Comparative Examples R1 and R5, the compositions of Examples 1 and 2 have improved and / or superior etch suppression performance on copper films and improved and / or superior etch selectivity of titanium nitride films relative to copper films.

[0237] Evaluation of Example 3

[0238] The composition of Example 1 was added to two beakers and heated to 50°C. A Co film was then immersed in one beaker for 5 minutes, and a titanium nitride film was immersed in the other beaker for 0.5 minutes. The thickness of the Co film was then measured using an XRF spectrometer (S8 Tiger, BRUKER) and the thickness of the titanium nitride film was measured using an ellipsometry (M-2000, JAWoolam). The etching rates (Å / min) of the composition for the Co film and the titanium nitride film were evaluated, and the etching rate for the titanium nitride film was divided by the etching rate for the Co film to evaluate R(TiN / Co). The results are summarized in Table 3.

[0239] The same experiment was repeated using the compositions of Example 2 and Comparative Examples R4 and R5, and the results are summarized in Table 3.

[0240] Table 3

[0241]

[0242] Referring to Table 3, it is confirmed that, compared with the compositions of Comparative Examples R4 and R5, the compositions of Examples 1 and 2 have improved and / or superior etch suppression performance on cobalt films and improved and / or superior etch selectivity of titanium nitride films relative to cobalt films.

[0243] Comparative examples R11 to R13

[0244] 25% by weight of hydrogen peroxide, 0.5% by weight of (NH4)2HPO4, 0.5% by weight of TMAH, and 0.1% by weight of EDTA, along with the amounts of the compounds shown in Table 4 as etching control agents, were weighed and mixed to prepare compositions of comparative examples R11 to R13. The remainder of each composition corresponds to water (deionized water).

[0245] Evaluation of Example 4

[0246] For comparative examples R11 to R13, pH, etching rate for Cu film (Å / min), etching rate for Co film (Å / min), etching rate for titanium nitride film (Å / min), R(TiN / Cu), and R(TiN / Co) were evaluated in the same manner as in evaluation examples 2 and 3, and the results are summarized together with the data from examples 1 and 2 in Table 4.

[0247] Table 4

[0248]

[0249]

[0250]

[0251]

[0252] Referring to Table 4, it is confirmed that compared with the compositions of Comparative Examples R11 to R13, the compositions of Examples 1 and 2 have improved and / or superior properties in terms of etching suppression performance of Cu film, etching selectivity of titanium nitride film relative to copper film, etching suppression performance of cobalt film, and etching selectivity of titanium nitride film relative to copper film.

[0253] According to one or more embodiments, the composition exhibits improved etch selectivity and improved cleaning performance, and is therefore more effectively used in various processing techniques for metal-containing films, such as etching and cleaning. In this respect, higher quality electronic devices, such as semiconductor devices, can be manufactured when the composition is used to process metal-containing films.

[0254] It should be understood that the embodiments described herein are to be considered in a descriptive sense only and are not intended for limiting purposes. The descriptions of features or aspects in each embodiment should typically be considered applicable to other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the accompanying drawings, those skilled in the art will understand that various changes in form and detail may be made therein without departing from the spirit and scope defined by the appended claims.

Claims

1. A composition comprising Oxidizing agent; Ammonium-based buffers; and Etching control agent, The etching control agent mentioned above comprises a compound represented by Formula 1. Formula 1 in, In Equation 1, R1 is C1-C 30 Alkyl or C2-C 30 alkenyl, R2 to R7 are each independently hydrogen, C1-C 30 Alkyl, or C2-C 30 alkenyl, L1 and L2 are each independently C1-C 30 Alkylene or C2-C 30 alkenyl, X and Z can each independently be hydrogen, alkali metal, or ammonium groups. At least one methylene group included in one or more of R1 to R7 is optionally replaced by O or S, and At least one hydrogen atom included in one or more of R1 to R7, L1, and L2 is optionally replaced by a halogen atom, hydroxyl group, thiol group, C1-C 30 alkoxy, or C1-C 30 Alkyl thio group substitution.

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

3. The composition according to claim 1, wherein the amount of the oxidant is in the range of 16% to 50% by weight, based on 100% by weight of the composition.

4. The composition according to claim 1, wherein... The ammonium-based buffer comprises N(A) 11 (A) 12 (A) 13 (A) 14 The ammonium group represented by ) and A 11 To A 14 Each independently is hydrogen, C1-C 30 Alkyl, C2-C 30 alkenyl, C3-C 30 Carbocyclic groups, or C1-C 30 Heterocyclic groups.

5. The composition of claim 1, wherein the ammonium-based buffer comprises at least one of hydroxide, acetate, bicarbonate, benzoate, carbonate, formate, nitrate, bisulfate, carbamate, aminosulfonate, citrate, phosphate, sulfite, sulfobenzoate, oxalate, lactate, tartrate, dihydrogen citrate, glutamate, salicylate, hydrogen oxalate, octanoate, propionate, glycolate, or gluconate.

6. The composition according to claim 1, wherein... The ammonium-based buffers include compounds represented by Formula 11-1, compounds represented by Formula 11-2, compounds represented by Formula 11-3, compounds represented by Formula 11-4, or any combination thereof: Formula 11-1 [N(A 11 )(A 12 )(A 13 )(A 14 )]3PO4 Formula 11-2 [N(A 11 )(A 12 )(A 13 )(A 14 )]2HPO4 Formula 11-3 [N(A 11 )(A 12 )(A 13 )(A 14 )]H2PO4 Formula 11-4 [N(A 11 )(A 12 )(A 13 )(A 14 )]OH in, In equations 11-1 to 11-4, A 11 To A 14 Each independently is hydrogen, C1-C 30 Alkyl, C2-C 30 alkenyl, C3-C 30 Carbocyclic groups, or C1-C 30 Heterocyclic groups.

7. The composition of claim 1, wherein the amount of the ammonium-based buffer is in the range of 0.01% to 10% by weight, based on 100% by weight of the composition.

8. The composition according to claim 1, wherein R1 in formula 1 is C5-C 30 Alkyl or C5-C 30 Alkenyl group.

9. The composition according to claim 1, wherein the atoms included in R1 of formula 1 are carbon and hydrogen.

10. The composition according to claim 1, wherein L1 and L2 in formula 1 are each independently C1-C4 alkylene groups.

11. The composition according to claim 1, wherein the amount of the etching control agent is in the range of 0.001% to 10% by weight, based on 100% by weight of the composition.

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

0.

13. A method for processing a metal-containing film, the method comprising: Prepare a substrate on which a metal-containing film is deposited; and The metal-containing film is brought into contact with the composition according to any one of claims 1 to 12.

14. The method of claim 13, wherein the metal in the metal-containing film 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.

15. The method of 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 according to claim 13, wherein, By contacting the metal-containing film with the composition, at least a portion of the metal-containing film is etched and / or cleaned.

17. The method of claim 13, wherein The metal-containing film has 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.

18. The method of claim 17, wherein the first region comprises Co, Cu, or a combination thereof, and the second region comprises titanium nitride.

19. The method of claim 13, wherein At least a portion of the metal-containing membrane is cleaned by contacting the metal-containing membrane with the composition and removing residues from the surface of the metal-containing membrane. The residues include etching gas residues, polymer residues, metal-containing residues, or any combination thereof.

20. A method for manufacturing an electronic device, the method comprising: Prepare a substrate on which a metal-containing film is deposited; The metal-containing film is brought into contact with the composition according to any one of claims 1 to 12; and The electronic device is manufactured by performing one or more subsequent manufacturing processes.

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