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

Abstract

Compositions, methods of treating metal-containing layers by using the compositions, and methods of manufacturing semiconductor devices by using the compositions are provided. The compositions can include an oxidizing agent, an ammonium-containing compound, and an etch control agent. The etch control agent can include a compound represented by Formula 1. A description of Formula 1 is provided herein.

Description

[0001] Cross-reference to related applications

[0002] This application is based on and claims priority to Korean Patent Application No. 10-2024-0177899 filed on December 3, 2024, and Korean Patent Application No. 10-2025-0107689 filed on August 5, 2025, the disclosures of which are incorporated herein by reference in their entirety. Technical Field

[0003] This disclosure relates to compositions, methods of treating metal-containing layers using the compositions, and / or methods of manufacturing semiconductor devices using the compositions. Background Technology

[0004] To meet consumers' demands for superior performance and low prices, increased integration and improved reliability of electronic devices (e.g., semiconductor devices) are required. With increased integration in semiconductor devices, damage to components during the semiconductor device manufacturing process can have a greater impact on the reliability and / or electrical characteristics of the semiconductor device. Specifically, during the semiconductor device manufacturing process, various processing techniques, such as etching and cleaning processes, can be applied to a given layer (e.g., a metal-containing layer). There is a persistent need for compositions that possess suitable etching rates and / or excellent cleaning capabilities for efficient metal-containing layer processing. Summary of the Invention

[0005] Provide a composition having improved and / or superior etch rate control performance, improved and / or superior cleaning performance, and improved and / or superior process stability; a method of treating a metal-containing layer using the composition; and / or a method of manufacturing a semiconductor device using the composition.

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

[0007] According to exemplary embodiments of this disclosure, the composition may include an oxidant, an ammonium-containing compound, and an etching control agent. The etching control agent may include a compound represented by Formula 1.

[0008] Formula 1

[0009]

[0010] In Equation 1,

[0011] L1 and L2 can each be a single bond or an oxygen atom, independently.

[0012] R1 can be hydrogen, C1-C 50 Alkyl or C2-C 50 alkenyl,

[0013] R2 and R3 can each be independently C1-C 50 Alkyl or C2-C 50 alkenyl, and

[0014] In R2, R3, and R1 when R1 is not hydrogen, C1-C 50 Alkyl and C2-C 50 At least one hydrogen atom in each of the alkenyl groups may optionally be replaced by a halogen atom.

[0015] In some implementations, the oxidant may include hydrogen peroxide.

[0016] In some embodiments, the ammonium-containing compound may include dihydrogen phosphate ([H2PO4]). - ), hydrogen phosphate ([HPO4]) 2- ), or phosphate ([PO4]) 3- ).

[0017] In some embodiments, in Formula 1, i) L1 may be oxygen and L2 may be a single bond, or ii) L1 and L2 may each be oxygen.

[0018] In some embodiments, R1 in Formula 1 may be hydrogen or a C1-C5 alkyl group.

[0019] In some implementations, in Equation 1, R2 and R3 can each be independently branched C3-C 50 alkyl.

[0020] In some embodiments, the etching control agent may further comprise an azole-containing compound, and the azole-containing compound may include a pyrazole group, an imidazole group, a triazole group, or a tetraazole group.

[0021] In some embodiments, the weight ratio of the compound represented by Formula 1 to the azole-containing compound may be selected from a range of 99:1 to 50:50.

[0022] According to exemplary embodiments of this disclosure, a method for processing a metal-containing layer may include:

[0023] Prepare a metal-containing layer comprising a first region and a second region, wherein the material in the first region of the metal-containing layer may differ from the material in the second region of the metal-containing layer; and

[0024] The metal-containing layer is brought into contact with the composition.

[0025] The first region of the metal-containing layer and the second region of the metal-containing layer may each independently include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), copper (Cu), cobalt (Co), tungsten (W), ruthenium (Ru), molybdenum (Mo), zinc (Zn), hafnium (Hf), or any combination thereof.

[0026] The composition may include an oxidant, an ammonium-containing compound, and an etching control agent.

[0027] Etching control agents include compounds represented by Formula 1.

[0028] In some embodiments, the first region of the metal-containing layer may include copper (Cu), cobalt (Co), tungsten (W), ruthenium (Ru), or any combination thereof.

[0029] In some embodiments, the second region of the metal-containing layer may include titanium nitride, titanium oxynitride, or any combination thereof.

[0030] In some embodiments, the second etching rate at which the composition etches the second region may be greater than the first etching rate at which the composition etches the first region.

[0031] According to exemplary embodiments of this disclosure, a method for manufacturing a semiconductor device may include:

[0032] Prepare a first insulating layer, a first conductive pattern in the first insulating layer, a second insulating layer on the first insulating layer, and an opening on the second insulating layer to form a mask pattern;

[0033] An opening is formed in the second insulating layer by etching a mask pattern using an opening;

[0034] The opening forms a mask pattern and the exposed surface inside the opening contacts the composition; and

[0035] A conductive material is provided in the opening, the conductive material being configured to be electrically connected to a first conductive pattern, wherein...

[0036] The composition may include an oxidant, an ammonium-containing compound, and an etching control agent, and

[0037] Etching control agents may include compounds represented by Formula 1.

[0038] In some embodiments, the first conductive pattern may include copper (Cu), cobalt (Co), tungsten (W), ruthenium (Ru), or any combination thereof.

[0039] In some implementations, the opening forming mask pattern may include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), or any combination thereof.

[0040] In some embodiments, the opening forming mask pattern may include metal nitrides, metal oxynitrides, or any combination thereof.

[0041] In some embodiments, the opening forming mask pattern may include titanium nitride, titanium oxynitride, or any combination thereof. Titanium nitride and titanium oxynitride may each optionally further include indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

[0042] In some embodiments, the first conductive pattern may include a first barrier layer pattern and a first fill layer on the first barrier layer pattern.

[0043] In some embodiments, during the formation of the opening, surface residues may be formed on at least one of the surface of the opening forming mask pattern and the exposed surface inside the opening, and the opening forming mask pattern and surface residues may be removed by contacting the opening forming mask pattern and the exposed surface inside the opening with the composition. Attached Figure Description

[0044] 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:

[0045] Figure 1 , 2A Figures 2 and 2B are schematic diagrams illustrating an embodiment of a method for processing a metal-containing layer;

[0046] Figure 3 It is a process flow diagram illustrating the implementation of a method for manufacturing electronic devices;

[0047] Figures 4A to 4J This is a cross-sectional view illustrating an embodiment of the process for forming trench and via hole patterns to form bit line electrodes;

[0048] Figure 5 These are photographs, where A represents the composition of Example 1 and B represents the composition of Comparative Example C1;

[0049] Figure 6A The images are scanning electron microscope (SEM) images of the interior of the opening observed after a cleaning (rinsing) and drying process using the composition of Example 1.

[0050] Figure 6B The image shows an SEM photograph of the interior of the opening after a cleaning and drying process, using the composition of Comparative Example C2.

[0051] Figures 7A to 7EThis is a schematic diagram illustrating a method for manufacturing a semiconductor device according to an embodiment; and

[0052] Figures 8 to 11 These are schematic diagrams used to describe semiconductor devices according to other embodiments. Detailed Implementation

[0053] The embodiments will now be described in detail, examples of which are illustrated 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 with reference to the accompanying drawings to illustrate aspects. As used herein, the singular forms “a” and “the” are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0054] As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items. Expressions such as “at least one of” when preceding or following a list of elements modify the entire list of elements but not any individual element of that list. 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.

[0055] When the terms “about” or “substantially” are used in conjunction with numerical values ​​in this specification, it is intended that the relevant numerical value includes manufacturing or operational tolerances (e.g., ±10%) around the stated numerical value. Furthermore, when the terms “generally” and “substantially” are used in conjunction with geometry, it is intended that precision of the geometry is not required, but tolerances for the shape are within the scope of this disclosure. Additionally, regardless of whether a numerical value or shape is modified to “about” or “substantially”, it will be understood that these values ​​and shapes should be interpreted as including manufacturing or operational tolerances (e.g., ±10%) around the stated numerical value or shape. When a range is specified, the range includes all values ​​within that range, for example, increments of 0.1%.

[0056] Although the term "equal to" is used in the description of the example implementation, it should be understood that some imprecision may exist. Therefore, when an element is said to be "equal to" another element, it should be understood that an element or value may be "equal to" another element within a range of expected manufacturing or operational tolerances (e.g., ±10%).

[0057] Metallic layer

[0058] The metals included in the metal layer may include alkali metals (e.g., sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), etc.), alkaline earth metals (e.g., beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), etc.), lanthanides (e.g., lanthanum (La), europium (Eu), terbium (Tb), ytterbium (Yb), etc.), and transition metals (e.g., scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (… (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), nickel (Ni), copper (Cu), silver (Ag), zinc (Zn), etc.), later transition metals (e.g., aluminum (Al), gallium (Ga), indium (In), thallium (Tl), tin (Sn), or bismuth (Bi), etc.), or any combination thereof.

[0059] According to one embodiment, the metal included in the metal-containing layer may include Ti, In, Al, La, Sc, Ga, Cu, Co, W, Ru, Mo, Zn, Hf, or any combination thereof.

[0060] According to another embodiment, the metal-containing layer may include two or more different metals.

[0061] According to another embodiment, the metal-containing layer may include metal, metal nitride, metal oxide, metal oxynitride, or any combination thereof.

[0062] According to another embodiment, the metal-containing layer may include titanium.

[0063] According to another embodiment, the metal-containing layer includes i) titanium (Ti), and optionally further includes ii) indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), silicon (Si), or any combination thereof. For example, the metal-containing layer may include titanium nitrides, titanium nitrides further including aluminum (e.g., TiAlN), titanium nitrides further including lanthanum, titanium nitrides further including silicon (e.g., TiSiN), etc.

[0064] According to another embodiment, the metal-containing layer may include a conductive metal (e.g., copper, cobalt, tungsten, ruthenium, etc.).

[0065] According to another embodiment, the metal-containing layer may include i) metal nitrides, metal oxynitrides, or any combination thereof (e.g., titanium nitrides, titanium oxynitrides, or any combination thereof) and ii) conductive metals (e.g., copper, cobalt, tungsten, ruthenium, etc.).

[0066] The metal-containing layer can be a single-layer structure comprising one or more materials, or a multi-layer structure comprising different materials. Multiple layers included in a multi-layer structure can be stacked vertically or arranged horizontally relative to the substrate. Both single-layer and multi-layer structures can have various three-dimensional patterns (e.g., vias, trenches, etc.).

[0067] Meanwhile, the metal-containing layer may include a first region and a second region, and the first region and the second region may each independently include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), copper (Cu), cobalt (Co), tungsten (W), ruthenium (Ru), molybdenum (Mo), zinc (Zn), hafnium (Hf), or any combination thereof, including that the material in the first region may be different from the material included in the second region.

[0068] According to one embodiment, the first region may include copper (Cu), cobalt (Co), tungsten (W), ruthenium (Ru), or any combination thereof.

[0069] According to another embodiment, the second region may include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), or any combination thereof.

[0070] According to another embodiment, the first region may include a conductive metal (e.g., copper, cobalt, tungsten, and ruthenium).

[0071] According to another embodiment, the second region may include metal nitrides, metal oxynitrides, or any combination thereof (e.g., titanium nitrides, titanium oxynitrides, or any combination thereof).

[0072] According to another embodiment, the second region may include titanium nitride, titanium oxynitride, or any combination thereof. Titanium nitride and titanium oxynitride may each optionally further include indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

[0073] According to another embodiment, the second region may include i) a titanium nitride, ii) a titanium oxynitride, iii) a titanium nitride further comprising indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof, iv) a titanium oxynitride further comprising indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof, or v) any combination thereof.

[0074] Composition

[0075] The composition may include an oxidant, an ammonium-containing compound, and an etching control agent.

[0076] The composition can be used in various processing techniques for metal-containing layers as described herein, such as etching, cleaning, and polishing processes.

[0077] The composition may further include water (e.g., deionized water).

[0078] According to one embodiment, the composition may not include a polishing agent.

[0079] According to another embodiment, the composition may not contain fluorine (F).

[0080] According to another embodiment, the composition may further include a pH adjuster. For example, the pH adjuster may be ammonium hydroxide, tetramethylammonium hydroxide (TMAH), etc., but is not limited thereto.

[0081] Throughout the specification, the term "etched layer" may refer to the removal of at least a portion of the material constituting the layer.

[0082] Oxidizing agent

[0083] An oxidizing agent is used to etch at least a portion of a metal-containing layer by oxidizing at least a portion of a metal (e.g., titanium) in the metal-containing layer to form a water-soluble complex, and may include at least one of, for example, hydrogen peroxide, nitric acid, and ammonium sulfate.

[0084] According to one embodiment, the oxidant may include hydrogen peroxide.

[0085] According to another embodiment, the oxidant may be hydrogen peroxide.

[0086] The amount (by weight) of oxidant relative to 100% by weight of the composition may be, for example, about 1% by weight to about 50% by weight, about 10% by weight to about 50% by weight, about 16% by weight to about 50% by weight, about 18% by weight to about 50% by weight, about 20% by weight to about 50% by weight, about 22% by weight to about 50% by weight, about 25% by weight to about 50% by weight, about 1% by weight to about 45% by weight, about 10% by weight to about 45% by weight, about 16% by weight to about 45% by weight, about 18% by weight to about 45% by weight, about 20% by weight to about 45% by weight, about 22% by weight to about 45% by weight, about 25% by weight to about 45% by weight, about 1% by weight to about 40% by weight, about 10% by weight to about 40% by weight, about 16% by weight to about 40% by weight, about 18% by weight to about 40% by weight, about 20% by weight to about 40% by weight. About 22% by weight to about 40% by weight, about 25% by weight to about 40% by weight, about 1% by weight to about 35% by weight, about 10% by weight to about 35% 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 1% by weight to about 30% by weight, about 10% by weight to about 30% 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.

[0087] When the amount of oxidant is within these ranges, the composition may have both improved and / or excellent etch selectivity and improved and / or excellent cleaning performance.

[0088] Ammonium-containing compounds

[0089] Ammonium-containing compounds can be used to maintain a high concentration of anions generated by an oxidant and to stabilize water-soluble complexes formed when the anions oxidize at least a portion of the metal (e.g., titanium) in a metal-containing layer. By using such ammonium-containing compounds, at least a portion of the metal-containing layer can be etched more effectively.

[0090] Ammonium-containing compounds may include an ammonium group.

[0091] According to one embodiment, the ammonium-containing compound may include N(A) 11 (A) 12 (A) 13 (A) 14 The ammonium group represented by ) is where A 11 To A14 Each can be independently hydrogen, C1-C 30 Alkyl, C2-C 30 alkenyl, C3-C 30 Carbocyclic groups, or C1-C 30 Heterocyclic groups.

[0092] For example, A 11 To A 14 Each can be independently hydrogen or C1-C 10 alkyl.

[0093] According to another embodiment, the ammonium-containing compound may not include fluorine (F). Without being limited by any particular theory, when the ammonium-containing compound does not include fluorine, accelerated corrosion of the surface of the metal-containing layer can be substantially limited and / or prevented, and the metal-containing layer treatment process using the composition can be carried out in a safe and environmentally friendly atmosphere.

[0094] According to another embodiment, the ammonium-containing compound may include 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.

[0095] According to another embodiment, the ammonium-containing compound may include a phosphate or a hydroxide.

[0096] According to another embodiment, the ammonium-containing compound may include dihydrogen phosphate ([H2PO4]). - ), hydrogen phosphate ([HPO4]) 2- ), or phosphate ([PO4]) 3- ).

[0097] According to another embodiment, the ammonium-containing compound may include the compound represented by formula 11-1, the compound represented by formula 11-2, the compound represented by formula 11-3, or any combination thereof:

[0098] Formula 11-1

[0099] [N(A 11 (A) 12 (A) 13 (A) 14 )]3PO4

[0100] Formula 11-2

[0101] [N(A 11 (A) 12 (A)13 (A) 14 )]2HPO4

[0102] Formula 11-3

[0103] [N(A 11 (A) 12 (A) 13 (A) 14 H2PO4

[0104] In equations 11-1 to 11-3, A 11 To A 14 Each can be the same as described in this article.

[0105] According to another embodiment, the ammonium-containing compound may include at least one of ammonium phosphate ((NH4)3PO4), diammonium monohydrogen phosphate ((NH4)2HPO4), diammonium dihydrogen phosphate ((NH4)H2PO4), [N(CH3)4]3PO4, di(tetramethylammonium monohydrogen phosphate) ([N(CH3)4]2HPO4), and tetramethylammonium dihydrogen phosphate ([N(CH3)4]H2PO4).

[0106] The amount (by weight) of the ammonium-containing compound relative to 100% of the composition can be, for example, 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 4% by weight, about 0.1% to about 4% by weight, about 0.3% to about 4% by weight, about 0.5% to about 4% by weight, about 0.01% to about 2% by weight, about 0.05% to about 10% by weight, and about 0.05% to about 10% by weight. From 0.1% to 2% by weight, from 0.1% to 2% by weight, from 0.3% to 2% by weight, from 0.5% to 2% by weight, from 0.01% to 1% by weight, from 0.05% to 1% by weight, from 0.1% to 1% by weight, from 0.3% to 1% by weight, from 0.5% to 1% by weight, from 0.01% to 0.7% by weight, from 0.05% to 0.7% by weight, from 0.1% to 0.7% by weight, from 0.3% to 0.7% by weight, from 0.5% to 0.7% by weight, from 0.01% to 0.5% by weight, from 0.05% to 0.5% by weight, from 0.1% to 0.5% by weight, or from 0.3% to 0.5% by weight.

[0107] When the amount of ammonium-containing compounds is within these ranges, the composition may have both improved and / or excellent etch selectivity and improved and / or excellent cleaning performance.

[0108] Etching control agent

[0109] Etching control agents can be used to control the etching rate (e.g., inhibit etching) by interacting with the atoms of individual metals (e.g., copper, cobalt, tungsten, ruthenium, etc.) in the metal-containing layer (which is the layer to be treated). Furthermore, etching control agents can be used to remove various surface residues generated during deposition and / or patterning processes of the metal-containing layer.

[0110] Etching control agents may include compounds represented by Formula 1:

[0111] Formula 1

[0112]

[0113] In Equation 1,

[0114] L1 and L2 can each be a single bond or an oxygen atom, independently.

[0115] R1 can be hydrogen, C1-C 50 Alkyl, or C2-C 50 alkenyl,

[0116] R2 and R3 can each be independently C1-C 50 Alkyl or C2-C 50 alkenyl, and

[0117] In R2, R3, and R1 when R1 is not hydrogen, C1-C 50 Alkyl and C2-C 50 At least one hydrogen atom in each of the alkenyl groups may optionally be replaced by a halogen atom.

[0118] C1-C 50 Alkyl and C2-C 50 Each alkenyl group can be either straight-chain or branched.

[0119] According to one embodiment, at least one of L1 and L2 in Formula 1 may be oxygen. Therefore, the metal atoms (e.g., copper, cobalt, tungsten, ruthenium, etc.) in the compound represented by Formula 1 and the metal-containing layer can be effectively coordinated and bonded to each other, such that a protective layer comprising the compound represented by Formula 1 can be suitably formed on the surface of the metal-containing layer. For example, in Formula 1, i) L1 may be oxygen and L2 may be a single bond, or ii) L1 and L2 may each be oxygen.

[0120] According to another embodiment, in Formula 1, R1 can be hydrogen or C1-C 20Alkyl group. For example, in formula 1, R1 can be hydrogen or C1-C2. 10 Alkyl group. As another example, in Formula 1, R1 can be hydrogen or a C1-C5 alkyl group (e.g., methyl, etc.).

[0121] According to another embodiment, in Equation 1, R2 and R3 can each be independently C1-C 20 Alkyl or C2-C 20 Alkenyl. For example, in Formula 1, R2 and R3 can each be independently C5-C. 20 Alkyl or C5-C 20 Alkenyl group.

[0122] According to another embodiment, in formula 1, R2 and R3 can each be C5-C 20 Alkyl, C5-C 10 Alkyl, C6-C9 alkyl, or C7-C8 alkyl.

[0123] According to another embodiment, in Equation 1, at least one of R2 and R3 (e.g., R2 and R3) can each independently be a branched C3-C 50 Alkyl, branched C3-C 20 Alkyl, branched C5-C 20 Alkyl, branched C5-C 10 Alkyl, branched C6-C9 alkyl, or branched C7-C8 alkyl.

[0124] According to another embodiment, in Equation 1, R2 and R3 can be the same as each other.

[0125] According to another embodiment, in Equation 1, R2 and R3 can be different from each other.

[0126] According to another embodiment, the etching control agent may include a compound represented by formula 1(1), a compound represented by formula 1(2), or any combination thereof:

[0127]

[0128] In Equations 1(1) and 1(2), R1 to R3 can each be the same as those described in this paper.

[0129] According to another embodiment, the etching control agent may include at least one of compounds 1 and 2:

[0130]

[0131] In Equation 1, R2 and R3 can each be independently represented as C1-C. 50 Alkyl or C2-C 50 Alkenyl. Furthermore, in Formula 1, C1-C 50 Alkyl or C2-C50 The hydrogens in each of the alkenyl groups (which can be R1 to R3) can be unsubstituted or C1-C. 50 Alkyl or C2-C 50 At least one hydrogen atom in each of the alkenyl groups (which can be R1 to R3) can be replaced by a halogen atom. Thus, for example, C1-C 50 Alkyl or C2-C 50 The alkenyl groups (which may be R1 to R3) may each exclude alkoxy, alkylthio, phosphate, amine derivative groups, etc., as substituents. Since a) R3 as defined above is a hydrophobic group and b) the group represented by *-L2-R2 (where L2 is a single bond) is a hydrophobic group, the compound represented by Formula 1 can provide a suitable hydrophobic protective layer to the surface of the metal-containing layer (which is the layer to be treated). Furthermore, by means of R2 and R3 as defined above, additional reactions between the hydrophobic protective layer and the surrounding metal ions can be substantially limited and / or suppressed, making the hydrophobic protective layer easier to remove along with various surface residues to be subsequently removed. Therefore, during contact of the metal-containing layer with the composition, the selective etching rate (e.g., etching suppression) for a given metal can be effectively controlled, while residues (surface residues and / or residues derived from (derived from) etching control agents) can remain substantially absent from the surface of the metal-containing layer. The descriptions of the terms “surface residue” and “residue derived from (etch control agent)” may be identical to those described herein.

[0132] Furthermore, compounds represented by Formula 1 having R2 and R3 as defined above can have large steric hindrance and are difficult to align regularly, making it virtually impossible to form micelles. Therefore, bubbles can be virtually avoided during the manufacture of the composition and / or when treating metal-containing layers using the composition. Since bubbles can lead to reduced efficiency and stability of metal-containing layer processing, wafer damage, residue regeneration, contamination of various equipment, etc., it is advantageous to limit and / or prevent bubble formation during the manufacture of the composition and / or when treating metal-containing layers using the composition. Without being limited by any particular theory, compositions in which bubble formation is observed during and / or immediately after manufacture may be substantially unsuitable for treating metal-containing layers, as bubbles can interfere with uniform contact between the composition and the metal-containing layer and can be a cause of additional residue formation on the surface of the metal-containing layer.

[0133] Therefore, by using the composition comprising the compound represented by Formula 1, the etching rate can be selectively controlled depending on the metal in the metal-containing layer without bubble formation, and at the same time, residues can be removed more effectively.

[0134] According to another embodiment, in addition to the compound represented by Formula 1, the etching control agent may further include an azole-containing compound.

[0135] In azole-containing compounds, the azole may contain two, three, or four nitrogen atoms as cyclic atoms.

[0136] According to another embodiment, the azole-containing compound may include a pyrazole group, an imidazole group, a triazole group, or a tetraazole group.

[0137] According to another embodiment, the azole-containing compound may include a pyrazole group.

[0138] According to another embodiment, the azole-containing compound may include compounds represented by Formula 2, Formula 3, Formula 4, Formula 5, Formula 6, Formula 7, Formula 8, Formula 9, or any combination thereof:

[0139] Formula 2

[0140]

[0141] Formula 3

[0142]

[0143] Formula 4

[0144]

[0145] Formula 5

[0146]

[0147] Formula 6

[0148]

[0149] Formula 7

[0150]

[0151] Formula 8

[0152]

[0153] Formula 9

[0154]

[0155] Among them, in equations 2 to 9,

[0156] X 11 It can be hydrogen, C1-C 50 Alkyl, C2-C 50 alkenyl or phenyl,

[0157] R 11 To R 17 Each can be independently hydrogen, halogen, nitro (-NO2), or C1-C. 50 Alkyl, C2-C 50 alkenyl or phenyl, and

[0158] In R 11 To R 17 And when X 11 X that is not hydrogen 11 In the middle, C1-C 50 Alkyl, C2-C 50 At least one hydrogen atom in each of the alkenyl and phenyl groups may optionally be replaced by a halogen atom.

[0159] According to another embodiment, X in formulas 2 to 9 11 It can be hydrogen.

[0160] According to another embodiment, R in formulas 2 to 9 11 To R 17 Each can be independently hydrogen, halogen, nitro (-NO2), or C1-C. 10 Alkyl, C2-C 10 Alkenyl or phenyl.

[0161] According to another embodiment, R in formulas 2 to 9 11 To R 17 Each can be independently hydrogen, nitro (-NO2), or C1-C4 alkyl (e.g., methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, etc.).

[0162] According to another embodiment, R in Equation 2 11 R 12 and R 13 At least one of them can be halogen, nitro (-NO2), C1-C 50 Alkyl, C2-C 50 Alkenyl or phenyl.

[0163] According to another embodiment, R in Equation 2 11 R 12 and R 13 At least one of them can be independently nitro (-NO2), C1-C 50 Alkyl or C2-C 50 Alkenyl group.

[0164] According to another embodiment, R in Equation 2 11 R 12 and R 13At least one of them can be halogen, nitro (-NO2), C1-C 10 Alkyl, C2-C 10 Alkenyl or phenyl.

[0165] According to another embodiment, R in Equation 2 11 R 12 and R 13 At least one of them can be independently nitro (-NO2), C1-C 10 Alkyl or C2-C 10 Alkenyl group.

[0166] According to another embodiment, R in Equation 2 11 R 12 and R 13 At least one of them may be nitro (-NO2) or C1-C4 alkyl (e.g., methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, etc.).

[0167] According to another embodiment, R in Equation 2 12 It can be halogen, nitro (-NO2), C1-C 10 Alkyl, C2-C 10 Alkenyl or phenyl.

[0168] According to another embodiment, R in Equation 2 12 It can be nitro (-NO2) or C1-C4 alkyl.

[0169] According to another embodiment, R in Equation 2 12 It can be nitro (-NO2) or C1-C4 alkyl, and R 11 and R 13 Each can be hydrogen.

[0170] According to another embodiment, R in formulas 3 to 9 14 To R 17 Each can be hydrogen.

[0171] According to another embodiment, the azole-containing compound may include a compound represented by Formula 2.

[0172] According to another embodiment, the azole-containing compound may include a compound represented by Formula 9.

[0173] According to another embodiment, the azole-containing compound may include at least one of compounds C5, C11, C12, C13, C14, C15, and C16:

[0174]

[0175]

[0176] According to another embodiment, the weight ratio of the compound represented by Formula 1 to the azole-containing compound can be selected from the range of 99:1 to 50:50, 95:5 to 50:50, or 90:10 to 50:50. For example, the weight ratio of the compound represented by Formula 1 to the azole-containing compound can be 65:35, 90:10, or 50:50.

[0177] According to another embodiment, relative to 100% by weight of the total amount of the compound represented by Formula 1 and the azole-containing compound, the amount (by weight) of the azole-containing compound may be about 5% by weight to about 60% by weight, about 10% by weight to about 60% by weight, about 5% by weight to about 50% by weight, or about 10% by weight to about 50% by weight.

[0178] By using azole-containing compounds in the composition in addition to those represented by Formula 1, the etching rate can be controlled more selectively depending on the metal in the metal-containing layer, and residues can be removed more effectively at the same time.

[0179] The amount (by weight) of the etching control agent relative to 100% by weight of the composition may be from about 0.001% by weight to about 10% by weight, from about 0.01% by weight to about 10% by weight, from about 0.1% by weight to about 10% by weight, from about 0.15% by weight to about 10% by weight, from about 0.2% by weight to about 10% by weight, from about 0.001% by weight to about 5% by weight, from about 0.01% by weight to about 5% by weight, from about 0.1% by weight to about 5% by weight, from about 0.15% by weight to about 5% by weight, from about 0.2% by weight to about 5% by weight, from about 0.001% by weight to about 1% by weight, from about 0.01% by weight to about 1% by weight. About 0.1 wt% to about 1 wt%, about 0.15 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 0.15 wt% to about 0.5 wt%, about 0.2 wt% to about 0.5 wt%, about 0.001 wt% to about 0.3 wt%, about 0.01 wt% to about 0.3 wt%, about 0.1 wt% to about 0.3 wt%, about 0.15 wt% to about 0.3 wt%, or about 0.2 wt% to about 0.3 wt%.

[0180] The compositions described above may have a pH range of 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 compositions is within these ranges, the interaction between the etching control agent and the metal atoms in the metal-containing layer, as described below, is more likely to occur.

[0181] According to embodiments, the composition can be used in metal-containing layer processing processes, such as etching processes, cleaning processes, etc., for metal-containing layers. The description of metal-containing layers is as follows.

[0182] Alternatively, the composition may also be used as an etching byproduct remover, a post-etching process byproduct remover, an ashing process byproduct remover, a cleaning composition, a photoresist (PR) remover, an etching composition for packaging processes, a cleaning agent for packaging processes, a wafer adhesive remover, an etchant, a post-etching residue stripper, an ashing residue cleaner, a PR residue stripper, or a post-CMP cleaner.

[0183] As used herein, the term "residue" refers to a material including at least one of "surface residue" and "residue derived from etching control agent".

[0184] As used herein, the term "surface residue" refers to a byproduct generated during the deposition and / or patterning of a metal-containing layer. Where surface residue remains on a metal-containing layer pattern formed after contact with the composition, the surface residue can cause an increase in resistance and / or an electrical short circuit between wirings. Surface residue can be etching residue resulting from an etching process, and can include, for example, residues derived from etching gases, residues derived from organic materials, metal-containing residues, or any combination thereof.

[0185] Residues originating from the etching gas may be residues from the etching gas used in dry etching. The etching gas may be, for example, a fluorocarbon gas. For instance, the etching gas may include CHF3, C2F6, CF4, C4F8, C2HF5, etc. Residues originating from the etching gas may include the etching gas itself and / or reaction products from the reaction between the etching gas and the materials in contact with it during the etching process.

[0186] Residues derived from organic materials may be organic polymers or organic-inorganic complexes (complexes) derived from various organic materials included in photoresists, dielectric layers, buffer layers, diffusion barrier layers, etc., used during the fabrication and / or patterning processes of metal-containing layers. For example, residues derived from organic materials may be polymers including carbon, silicon, fluorine, or any combination thereof.

[0187] Metallic residues may be any residues of metal that have separated from the metallic layer during the manufacturing and / or patterning process of the metallic layer.

[0188] As used herein, the expression "residue derived from etch control agent" refers, for example, to aggregates comprising the etch control agent that are insoluble in water due to their high molecular weight and remain on the surface of the metal-containing layer even after cleaning and / or drying processes following contact between the composition and the metal-containing layer. Where residues derived from the etch control agent remain on the pattern of the metal-containing layer, these residues can lead to increased resistance and / or electrical short circuits between wirings.

[0189] Methods for processing metal-containing layers and methods for manufacturing electronic devices

[0190] By using the above composition, metal-containing layers can be processed more effectively. The metal-containing layer includes a first region and a second region, wherein the material in the first region is different from the material included in the second region.

[0191] Therefore, a method for processing a metal-containing layer is provided, the method comprising: preparing a substrate on which a metal-containing layer including a first region and a second region is provided, and contacting the metal-containing layer with the composition. The metal-containing layer, the first region, and the second region are as described in the specification.

[0192] According to the implementation, the first region and the second region may each independently include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), copper (Cu), cobalt (Co), gallium (Ga), tungsten (W), ruthenium (Ru), molybdenum (Mo), zinc (Zn), hafnium (Hf), or any combination thereof.

[0193] According to one embodiment, the first region may include copper (Cu), cobalt (Co), tungsten (W), ruthenium (Ru), or any combination thereof.

[0194] According to another embodiment, the second region may include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), or any combination thereof.

[0195] According to another embodiment, the first region may include a conductive metal (e.g., copper, cobalt, tungsten, ruthenium, or any combination thereof), and the second region may include a metal nitride, a metal oxynitride, or any combination thereof.

[0196] According to another embodiment, the second region may include titanium nitride, titanium oxynitride, or any combination thereof. Titanium nitride and titanium oxynitride may each optionally further include indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

[0197] For example, the second region may include i) titanium nitride, ii) titanium oxynitride, iii) further including titanium nitride of indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si) or any combination thereof, iv) further including titanium oxynitride of indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si) or any combination thereof, or v) any combination thereof.

[0198] According to another embodiment, the first region may include copper (Cu), cobalt (Co), tungsten (W), ruthenium (Ru), or any combination thereof, and the second region may include titanium nitride, titanium oxynitride, or any combination thereof.

[0199] According to another embodiment, 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. Therefore, when both the first and second regions of the metal-containing layer are in contact with the composition simultaneously, the second region can be etched faster than the first region. For example, by controlling the content ratio of the compounds included in the composition, the contact time between the composition and the metal-containing layer, at least a portion or the entire second region can be etched without over-etching (e.g., substantial etching) of the first region.

[0200] According to another embodiment, a second region of the metal-containing layer can be removed (e.g., substantially removed) by a process of contacting the metal-containing layer with the composition.

[0201] According to another embodiment, surface residues are present on the metal-containing layer, and the second region of the metal-containing layer and the surface residues present thereon can be removed (e.g., substantially removed) by a process of contacting the metal-containing layer with the composition.

[0202] Figure 1 , 2A Figures 2B and 2B are schematic diagrams illustrating a method for processing a metal-containing layer according to an embodiment.

[0203] like Figure 1 As shown, a substrate 10 is provided having a metal-containing layer 20A. Although in Figure 1 Various circuit elements may be optionally disposed between the substrate 10 and the metal-containing layer 20A, but are not shown in the figure.

[0204] The substrate 10 may be a silicon substrate, a gallium arsenide substrate, a silicon-germanium substrate, a ceramic substrate, a quartz substrate, a glass substrate for display, a semiconductor substrate, or a semiconductor-on-insulator (SOI) substrate.

[0205] Figure 1The metal-containing layer 20A may include a first region 21 and a second region 22. The first region 21 and the second region 22 may be arranged to be spaced apart from each other or at least partially overlap each other, and the metal-containing layer 20A may have various patterns. The metal-containing layer 20A, the first region 21 and the second region 22 are as described in the specification.

[0206] For example, the first region 21 may include copper (Cu), cobalt (Co), tungsten (W), ruthenium (Ru), or any combination thereof, and the second region 22 may include titanium nitride, titanium oxynitride, or any combination thereof.

[0207] Surface residue R may exist Figure 1 The surface of the metal-containing layer 20A. Surface residue R, as a byproduct generated during the deposition and / or patterning of the metal-containing layer 20A, can be a substance that, if remaining on the metal-containing layer pattern 20, can lead to increased resistance and / or electrical short circuits between wirings. Surface residue R is as described in the specification regarding "surface residue".

[0208] like Figure 1 As shown, a metal-containing layer 20A, including a first region 21 and a second region 22 and having surface residue R, is brought into contact with composition 30. As a result, at least a portion of the metal-containing layer 20A can be etched, and the surface residue R can be removed by composition 30. Composition 30 includes an oxidant, an ammonium-containing compound, and an etching control agent as described above. A detailed description of this is provided in the specification. Providing composition 30 to make contact between the metal-containing layer 20A and composition 30 can be achieved by using various methods such as dipping, coating, and spraying.

[0209] In composition 30, i) an oxidant can be used to etch at least a portion of the metal-containing layer 20A (e.g., at least the second region 22) by oxidizing at least a portion of the metal in the metal-containing layer 20A to form a water-soluble complex; ii) an ammonium-containing compound can be used to maintain a high concentration of anions generated by the oxidant and to effectively etch at least a portion of the metal-containing layer 20A (e.g., at least the second region 22) by stabilizing the water-soluble complex generated when the anions oxidize at least a portion of the metal in the metal-containing layer 20A; and iii) an etching control agent comprising a compound represented by Formula 1 having R2 and R3 as defined above can be used to selectively control the etching rate depending on the metal in the metal-containing layer 20A by selectively forming a hydrophobic protective layer without bubble formation, and simultaneously more effectively remove surface residues R generated during the deposition process and / or patterning process of the metal-containing layer 20A. Therefore, composition 30 as described above can be usefully used in various processing techniques for the metal-containing layer 20A.

[0210] According to another embodiment, when in contact with the composition 30, the surface of the first region 21 is substantially protected, and the second etching rate at which the composition 30 etches the second region 22 can be greater than the first etching rate at which the composition 30 etches the first region 21.

[0211] As a result, when the first region 21 and the second region 22 of the metal-containing layer 20A are simultaneously in contact with the composition 30, the second region 22 can be etched faster than the first region 21. For example, by controlling the content ratio of the compounds included in the composition 30, the contact time between the composition 30 and the metal-containing layer 20A, etc., without over-etching (e.g., substantial etching) of the first region 21, it is possible to achieve the desired effect. Figure 2A At least a portion of the second region 22 shown in the figure may be etched as follows Figure 2B The entire second region 22 is etched as shown, thereby forming as Figure 2A Or the metal-containing layer pattern 20 shown in 2B.

[0212] Furthermore, in the absence of bubble formation, composition 30, comprising a compound represented by Formula 1 as an etching control agent, can effectively remove both surface residues R generated during the deposition and / or patterning processes of the metal-containing layer 20A and residues derived from the etching control agent. Therefore, the residues (i.e., Figure 1 Surface residues (R) and / or residues derived from etching control agents may be substantially absent. Figure 2A and 2B The metallic layer pattern 20 is on the surface of the surface. For example, it can be confirmed by transmission electron microscopy (TEM) analysis, scanning electron microscopy (SEM) analysis, etc. Figure 2A and 2B The presence or absence of residues (i.e., surface residues R and / or residues derived from etching control agents) on the metal-containing layer pattern 20.

[0213] Therefore, by using a composition comprising an oxidant, an ammonium-containing compound, and an etching control agent as described herein, it is possible to simultaneously achieve both improved etching rate and / or superior etching selectivity for a given metal and improved and / or superior residue removal, and thus to process metal-containing layers efficiently and at low cost.

[0214] refer to Figure 3 The method for manufacturing an electronic device according to the embodiments may include: preparing a substrate S100 on which a metal-containing layer is provided; contacting the metal-containing layer with a composition S110; and performing at least one subsequent manufacturing process to manufacture the electronic device S120.

[0215] Electronic devices can be, for example, various semiconductor devices.

[0216] Therefore, according to the embodiment, the substrate S100 on which the metal-containing layer is provided and the contact S110 between the metal-containing layer and the composition can be used in the process of forming openings (e.g., trenches, via patterns, etc.) for bit line electrodes in a method of manufacturing a semiconductor device.

[0217] The following is for reference. Figures 4A to 4J The following describes an embodiment of a trench and via pattern forming process using the composition to form bit line electrodes.

[0218] Figure 4A A portion of a semiconductor substrate (transistor, etc., not shown) including a first dielectric layer 103 and a metal layer 101 is illustrated. The metal layer 101 may include at least one of, for example, Co and Cu. 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, tantalum, Ti, W, tantalum nitride, TiN, tungsten nitride, or any combination thereof.

[0219] The second diffusion barrier layer 107 can be arranged in... Figure 4A The first dielectric layer 103 and the metal layer 101 are on the first dielectric layer 103 and the second diffusion barrier layer 107, which may include, for example, silicon nitride or nitrogen-doped silicon carbide.

[0220] 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.

[0221] 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.

[0222] Available Figure 4A A hard mask layer 113 is disposed on the buffer layer 111. The hard mask layer 113 may include i) titanium nitride (TiN), ii) titanium nitrides further including In, Al, La, Sc, Ga, Zn, Hf, or any combination thereof (e.g., TiAlN), or iii) any combination thereof. For example, the hard mask layer 113 may include titanium nitride.

[0223] The first photoresist 115 can be applied to... Figure 4A On the hard mask layer 113.

[0224] Next, the first photoresist 115 can be patterned to form a first photoresist 115 pattern having a first opening with a width t, such as Figure 4B As shown. Then, as Figure 4CAs shown, the hard mask layer 113 can be etched according to the pattern of the first photoresist 115 to open a portion of the buffer layer 111, and then as... Figure 4D As shown, the pattern of the first photoresist 115 can be removed, for example, by ashing, to form an exposed hard mask layer 113 pattern.

[0225] Next, as Figure 4E As shown, a filler layer 117 may be formed to cover the pattern of the hard mask layer 113, thereby filling the openings in the pattern of the hard mask layer 113. The filler layer 117 may include, for example, hydrogen silsesquioxane (HSQ) or methyl silsesquioxane (MSQ).

[0226] After that, as Figure 4F As shown, a second photoresist 119 can be formed on the filler layer 117. The second photoresist 119 can then be patterned to form a second photoresist 119 pattern having a second opening with a width v, as shown. Figure 4G As shown in the diagram. Then, for example, using reactive ion etching (RIE), 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 disposed beneath the second photoresist 119 pattern can be etched to partially form vias, such as... Figure 4H As shown in the figure, the second photoresist 119 pattern and filler layer 117 can then be removed.

[0227] Next, as Figure 4I As shown, according to the pattern of the hard mask layer 113, the buffer layer 111, the second dielectric layer 109, and the second diffusion barrier layer 107 can be etched using, for example, a dry etching process until the vias reach the metal layer 101, thereby forming trench and via patterns. The etching gas used in the dry etching process can be, for example, a fluorocarbon gas (e.g., CHF3, C2F6, CF4, C4F8, C2HF5, etc.).

[0228] As a result of dry etching, a significant amount of surface residue R can exist on the inner walls of trenches and via patterns, such as... Figure 4IAs shown in the diagram. Surface residue R may include residues derived from etching gases, residues derived from organic materials, metal-containing residues, or any combination thereof. Residues derived from etching gases may include the etching gas itself and / or reaction products with any material (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. Residues derived from organic materials may be polymers derived from various organic substances included in the second photoresist 119, second dielectric layer 109, buffer layer 111, second diffusion barrier layer 107, etc. For example, residues derived from organic materials may be polymers including carbon, silicon, fluorine, or any combination thereof. Metal-containing residues may be, for example, residues of metals included in the pattern of hard mask layer 113.

[0229] Figure 4I The surface residue R should be removed because it increases the resistance of the semiconductor device or causes an electrical short circuit in the bit line electrodes formed later. Simultaneously, to simplify the process, the surface residue R and the hard mask layer 113 pattern can be removed at the same time. Furthermore, the metal layer 101 should be substantially undamaged when removing the surface residue R and the hard mask layer 113 pattern.

[0230] Therefore, by mixing the composition described above, which includes an oxidant, an ammonium-containing compound, and an etching control agent, with... Figure 4I The substrate contacts (the substrate includes a metal-containing layer, the metal-containing layer includes a hard mask layer 113 pattern and a metal layer 101) i) can remove surface residue R generated on the inner walls of the trench and via patterns, ii) can remove the hard mask layer 113 pattern, and iii) can substantially avoid damaging the metal layer 101, thereby manufacturing Figure 4J The substrate. Not limited by any particular theory, for example, the pattern of the hard mask layer 113 can be removed by an oxidant and an ammonium-containing compound, the surface residue R can be removed by an etching control agent, and simultaneously, the metal layer 101 can be substantially unetched. Afterwards, metallic materials, etc., can be filled into... Figure 4J In the groove and through-hole patterns, to form bit line electrodes, etc.

[0231] Methods for manufacturing semiconductor devices

[0232] The composition can be effectively used in methods for manufacturing semiconductor devices.

[0233] In the following text, reference will be made to Figures 7A to 7E A method for manufacturing a semiconductor device using a composition according to an embodiment is described.

[0234] First, such as Figure 7AAs shown, a substrate 100 is prepared having a first insulating layer 131, a first conductive pattern 121 disposed in the first insulating layer 131, a second insulating layer 132 disposed on the first insulating layer 131, and an opening disposed on the second insulating layer 132 forming a mask pattern 122.

[0235] Substrate 100 as referenced Figure 1 The substrate 10 is described. Although in Figure 7A Not shown, but substrate 100 may include various semiconductor devices, transistors, etc. For example, semiconductor devices may include memory semiconductors or non-memory semiconductors. Memory semiconductors may be i) volatile memories such as dynamic random access memory (DRAM) or static random access memory (SRAM), or ii) non-volatile memories such as electrically erasable programmable read-only memory (EEPROM), flash memory (also considered a subset of EEPROM), or NAND. Non-memory semiconductors may be microcomponents (e.g., microcontrollers including processing circuitry), analog integrated circuits (ICs), logic ICs, or optical semiconductors. Transistors may have a planar structure, a fin field-effect transistor (FinFET) structure, or a gate-all-around (GAA) structure.

[0236] The insulating material included in each of the first insulating layer 131 and the second insulating layer 132 may include various oxides, nitrides, oxynitrides, high-dielectric materials, or any combination thereof. For example, the insulating material may include silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, hafnium oxide, hafnium oxynitride, zirconium oxide, or any combination thereof. Hafnium oxide and hafnium oxynitride may optionally further include Si, Ta, Ti, Zr, or any combination thereof. As another example, the insulating material may include tetraethyl orthosilicate (TEOS), hydrogen silsesquioxane (HSQ), methyl silsesquioxane (MSQ), etc. The first insulating layer 131 and the second insulating layer 132 may be formed as separate (separate) layers (e.g., Figure 7A (As shown in the figure) or it can be formed as an integral layer and can be modified in various ways.

[0237] Although not in Figure 7A As shown, an etch stop layer may be additionally disposed between the first insulating layer 131 and the second insulating layer 132. For example... Figure 7B As shown, the etch stop layer may define an etch stop line and limit and / or prevent damage to the first insulating layer 131 during the etch process used to form the opening OP in the second insulating layer 132. The etch stop layer may include aluminum oxide, silicon nitride, silicon oxynitride, silicon carbon nitride, or any combination thereof.

[0238] For the material included in the first conductive pattern 121, see the description of the material included in the first region of the metal-containing layer. For the material included in the opening forming mask pattern 122, see the description of the material included in the second region of the metal-containing layer. The first conductive pattern 121 may be, for example, wiring, vias, etc.

[0239] According to one embodiment, the first conductive pattern 121 may include copper (Cu), cobalt (Co), tungsten (W), ruthenium (Ru), or any combination thereof.

[0240] According to another embodiment, the opening forming mask pattern 122 may include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), or any combination thereof.

[0241] According to another embodiment, the opening forming mask pattern 122 may include metal nitrides, metal oxynitrides, or any combination thereof.

[0242] According to another embodiment, the opening forming mask pattern 122 may include titanium nitride, titanium oxynitride, or any combination thereof. The titanium nitride and titanium oxynitride may each optionally further include indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof. For example, the opening forming mask pattern 122 may include i) titanium nitride, ii) titanium oxynitride, iii) titanium nitride further including indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof, iv) titanium oxynitride further including indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof, or v) any combination thereof.

[0243] According to another embodiment, the first conductive pattern 121 may include copper (Cu), cobalt (Co), tungsten (W), ruthenium (Ru), or any combination thereof, and the opening forming mask pattern 122 may include titanium nitride, titanium oxynitride, or any combination thereof.

[0244] Subsequently, as Figure 7B As shown, the second insulating layer 132 is etched using the opening forming mask pattern 122 to form the opening OP in the second insulating layer 132. In other words, the second insulating layer 132 can be etched along the opening forming mask pattern 122 or through the opening region of the opening forming mask pattern 122 to form the opening OP in the second insulating layer 132. Figure 7BAs shown, the inner wall of the opening OP may be defined by the surface of the first conductive pattern 121 and the surface of the second insulating layer 132. The etching process may be, for example, a dry etching process using an etching gas. The etching gas may be, for example, a fluorocarbon gas. For example, the etching gas may include hydrofluorocarbons such as CHF3, C2F6, CF4, C4F8, C2HF5, etc. In this case, as... Figure 7B As shown, surface residue R may be formed on the surface of the opening forming mask pattern 122 and / or in the opening OP in which the surface of the first conductive pattern 121 is exposed. Surface residue R is as described in the specification. The opening OP may be, for example, a trench, a hole, etc.

[0245] Subsequently, as Figure 7C As shown, the opening forms a mask pattern 122 and the interior of the opening OP (e.g., the exposed surface of the interior of the opening OP) comes into contact with the composition 30. The composition 30 may include the oxidant, ammonium-containing compound, and etching control agent as described above, and a detailed description thereof is provided in the specification.

[0246] In composition 30, i) an oxidant can be used to etch and remove the opening-forming mask pattern 122 by oxidizing the metal (e.g., titanium) in the opening-forming mask pattern 122 to form a water-soluble complex; ii) an ammonium-containing compound can be used to maintain a high concentration of anions generated by the oxidant and to effectively etch and remove the opening-forming mask pattern 122 by stabilizing the water-soluble complex generated when the anions oxidize the metal (e.g., titanium) in the opening-forming mask pattern 122; and iii) an etching control agent comprising a compound represented by formula 1 having R2 and R3 as defined above can be used to selectively control the etching rate by forming a hydrophobic protective layer on the first conductive pattern 121 to suppress over-etching (e.g., substantial etching) of the first conductive pattern 121 without bubble formation, while simultaneously effectively removing surface residues R generated inside the opening OP during the formation of the opening OP.

[0247] For example, when the interior of the opening forming mask pattern 122 and the opening OP is in contact with the composition 30, the surface of the first conductive pattern 121 can be substantially protected, and therefore the second etching rate of the composition 30 etching the opening forming mask pattern 122 can be greater than the first etching rate of the composition 30 etching the first conductive pattern 121, thereby etching and removing the opening forming mask pattern 122 without over-etching (e.g., substantial etching) of the first conductive pattern 121. Figure 7D As shown in the image.

[0248] Furthermore, composition 30, comprising a compound represented by Formula 1, can effectively remove both surface residue R and residues originating from the etching control agent without forming bubbles. Therefore, the residues (i.e., Figure 7CSurface residues (R) and / or residues derived from etching control agents may be substantially absent. Figure 7D The interior of the opening OP and the surface of the second insulating layer 132. For example, the presence or absence of residues can be confirmed by transmission electron microscopy (TEM) analysis, scanning electron microscopy (SEM) analysis, etc.

[0249] Therefore, by using a composition comprising an oxidant, an ammonium-containing compound, and an etching control agent as described herein, selective etching of the opening-forming mask pattern 122 without substantially etching the surface of the first conductive pattern 121 and efficient removal of residues from the interior of the opening OP can be achieved simultaneously, and thus the opening OP can be patterned efficiently and at low cost.

[0250] Subsequently, conductive material is introduced into the opening OP in a configuration to be electrically connected to the first conductive pattern 141 to form a second conductive pattern 142 that is in contact with the second insulating layer 132 and electrically connected to the first conductive pattern 121, such as... Figure 7E As shown in the diagram. The second conductive pattern 142 can be, for example, wiring, vias, etc.

[0251] The conductive material and the second conductive pattern 142 may include copper (Cu), carbon (C), silver (Ag), cobalt (Co), tantalum (Ta), indium (In), tin (Sn), zinc (Zn), manganese (Mn), titanium (Ti), magnesium (Mg), chromium (Cr), germanium (Ge), strontium (Sr), platinum (Pt), aluminum (Al), zirconium (Zr), tungsten (W), ruthenium (Ru), iridium (Ir), rhodium (Rh), or any combination thereof. Optionally, the conductive material and the second conductive pattern 142 may further include titanium (Ti), titanium nitride (TiN), tantalum (Ta), tantalum nitride (TaN), tantalum carbonitride (TaCN), tungsten (W), tungsten nitride (WN), tungsten carbonitride (WCN), zirconium (Zr), zirconium nitride (ZrN), vanadium (V), vanadium nitride (VN), niobium (Nb), niobium nitride (NbN), or any combination thereof. The second conductive pattern 142 can be formed by using various methods such as atomic layer deposition (ALD) and chemical vapor deposition (CVD).

[0252] Figure 8 A semiconductor device according to another embodiment is schematically shown, which is related to... Figure 7E The semiconductor device shown is the same, except that the first conductive pattern 121 includes a first barrier layer pattern 121B and a first fill layer 121F disposed on the first barrier layer pattern 121B. The first barrier layer pattern 121B and the first fill layer 121F may comprise different materials. For example, the first barrier layer pattern 121B may comprise cobalt, and the first fill layer 121F may comprise copper, but are not limited thereto. Reference can be made to the manufacturing process. Figure 7EThe description of the method for manufacturing the semiconductor device shown is used to understand the process. Figure 8 The method for constructing a semiconductor device, in addition to forming a first barrier layer pattern 121B and then forming a first fill layer 121F on the first barrier layer pattern 121B during the formation of a first conductive pattern 121.

[0253] Figure 9 A semiconductor device according to another embodiment is schematically shown, which is related to... Figure 7E The semiconductor device shown is the same, except that the second conductive pattern 142 includes a second barrier layer pattern 142B and a second fill layer 142F disposed on the second barrier layer pattern 142B. The second barrier layer pattern 142B and the second fill layer 142F may include different materials. For example, the second barrier layer pattern 142B may include cobalt (Co), titanium (Ti), titanium nitride (TiN), tantalum (Ta), tantalum nitride (TaN), tantalum carbonitride (TaCN), tungsten (W), tungsten nitride (WN), tungsten carbonitride (WCN), zirconium (Zr), zirconium nitride (ZrN), vanadium (V), vanadium nitride (VN), niobium (Nb), niobium nitride (NbN), or any combination thereof. The second filler layer 142F may include copper (Cu), carbon (C), silver (Ag), cobalt (Co), tantalum (Ta), indium (In), tin (Sn), zinc (Zn), manganese (Mn), titanium (Ti), magnesium (Mg), chromium (Cr), germanium (Ge), strontium (Sr), platinum (Pt), aluminum (Al), zirconium (Zr), tungsten (W), ruthenium (Ru), iridium (Ir), rhodium (Rh), or any combination thereof. As another example, the second barrier layer pattern 142B may include a combination of cobalt and tantalum nitride, a combination of cobalt and titanium nitride, or cobalt, and the second filler layer 142F may include copper, but is not limited thereto. Reference can be made to the manufacturing process. Figure 7E The description of the method for manufacturing the semiconductor device shown is used to understand the process. Figure 9 The method for constructing a semiconductor device, in addition to forming a second barrier layer pattern 142B and then forming a second fill layer 142F on the second barrier layer pattern 142B during the formation of a second conductive pattern 142.

[0254] Figure 10 A semiconductor device according to another embodiment is schematically shown, which is related to... Figure 9 The semiconductor device shown is the same, except that the second barrier layer pattern 142B has an opening corresponding to the surface of the first conductive pattern 121. See manufacturing process. Figure 9 The description of the method for manufacturing the semiconductor device shown is used to understand the process. Figure 10 The method for constructing a semiconductor device, in addition to the process of adding an opening to the surface corresponding to the first conductive pattern 121 during the formation of the second barrier layer pattern 142B.

[0255] Figure 11 A semiconductor device according to another embodiment is schematically shown, which is related to... Figure 9 The semiconductor device shown is the same, except that the second barrier layer pattern 142B includes a first layer 142B1 having an opening on the surface corresponding to the first conductive pattern 121 and a second layer 142B2 disposed on the first layer 142B1 and covering the first conductive pattern 121. For example, the first layer 142B1 may include titanium nitride, tantalum nitride, or any combination thereof, and the second layer 142B2 may include cobalt (Co). Reference can be made to the manufacturing process. Figure 9 The description of the method for manufacturing the semiconductor device shown is used to understand the process. Figure 11 The method for constructing a semiconductor device, in addition to forming a first layer 142B1 having an opening on a surface corresponding to a first conductive pattern 121, and then forming a second layer 142B2.

[0256] Examples 1 to 5 and Comparative Examples C1 to C6

[0257] The compositions of Examples 1 to 5 and Comparative Examples C1 to C6 were prepared by mixing 25% by weight of hydrogen peroxide, 0.5% by weight of (NH4)2HPO4 etching control agent, and tetramethylammonium hydroxide (TMAH) in an amount selected in the range of 0.01% to 0.5% by weight. The materials and amounts listed in Table 1 were used as etching control agents in the compositions. The amount of TMAH in each composition was selected to adjust the pH of each composition to 7.5, and the remainder of the composition corresponded to water (deionized water).

[0258] Comparative Example C7

[0259] The composition was prepared in the same manner as in Example 1, except that no etching control agent was used.

[0260] Evaluation Example 1

[0261] After manufacturing the compositions of Examples 1 to 5 and Comparative Examples C1 to C7 respectively, bubble formation was visually evaluated, and the results are summarized in Table 1. Figure 5 These are photographs, where A shows the composition of Example 1 and B shows the composition of Comparative Example C1.

[0262] [Table 1]

[0263]

[0264] For "N" indicating bubble formation: No bubbles were observed.

[0265] For the "Y" shape representing bubble formation: Bubbles are observed.

[0266]

[0267]

[0268]

[0269] Depend on Figure 5 It was confirmed that no bubble formation was observed in the composition of Example 1, but bubble formation was observed in the composition of Comparative Example C1. Similarly, no bubble formation was observed in the compositions of Examples 2 to 5, as in the composition of Example 1, and bubble formation was observed in the compositions of Comparative Examples C3 and C6, as in the composition of Comparative Example C1.

[0270] from Figure 5 As confirmed by Table 1, the compositions of Comparative Examples C1, C3, and C6 are not suitable for processing metal-containing layers because bubble formation was observed after the composition was manufactured. Therefore, the remaining compositions, namely the compositions of Examples 1 to 5 and Comparative Examples C2, C4, C5, and C7, were used to conduct Evaluation Example 2 as follows.

[0271] Evaluation Example 2

[0272] like Figure 7B As shown, a substrate was prepared comprising a first conductive pattern disposed in a first insulating layer, an opening formed in a second insulating layer, and an opening on the second insulating layer forming a mask pattern. In the substrate, the first and second insulating layers were formed using silicon oxide, the openings were formed using titanium nitride to form the mask pattern, the first conductive pattern was formed using copper, and the openings were formed using CHF3 etching gas. Subsequently, the substrate was immersed in an immersion bath containing the composition of Example 1 at 25°C for 5 minutes, followed by a cleaning and drying process. The presence or absence of residues in the openings was then observed using a scanning electron microscope (SEM) to evaluate the residue removal performance of the composition of Example 1, and the results are shown in Table 2. Additionally, the pH of the composition of Example 1 was evaluated using a pH meter, and the results are summarized in Table 2.

[0273] Subsequently, the composition of Example 1 was placed in two separate beakers and heated to 50°C. Copper and cobalt films, which had undergone immersion in a mixture of HF and water at a volume ratio of 1:200 for 40 seconds at room temperature, were then immersed in the beakers for 10 minutes and 5 minutes, respectively. The thicknesses of the copper and cobalt films were then measured using X-ray fluorescence spectroscopy (XRF) (S8 Tiger, BRUKER) to evaluate the etching rate (Å / min) of the copper film and the cobalt film of Example 1. The results are summarized in Table 2.

[0274] The compositions of Examples 2 to 5 and Comparative Examples C2, C4, C5 and C7 were tested repeatedly, and the results are summarized in Table 2. Figure 6A These are SEM images of the interior of the opening observed after the cleaning and drying process in Example 1, and Figure 6B These are SEM images of the interior of the opening observed using comparative example C2 after the cleaning and drying process. Figure 6A and 6B In the figure, the first conductive pattern is indicated by reference numeral "101".

[0275] [Table 2]

[0276]

[0277] "Good" residue removal: No residues with a length of 10 nm or longer were observed.

[0278] Poor residue removal: Residues with a length of 10 nm or longer were observed.

[0279]

[0280]

[0281] exist Figure 6A In the middle, virtually no residue was observed, but Figure 6B Residues were observed as "R" markings. (By...) Figure 6A and 6B It was confirmed that the composition of Example 1 had good cleaning performance, while the composition of Comparative Example C2 had poor cleaning performance. Similarly, as with the composition of Example 1, no residue was observed inside the openings that came into contact with the compositions of Examples 2 to 5, while as with the composition of Comparative Example C2, residue was observed inside the openings that came into contact with the compositions of Comparative Examples C4, C5, and C7, respectively. Figure 6A and 6B As can be confirmed by Table 2, the compositions of Examples 1 to 5 have superior residue removal performance compared with the compositions of Comparative Examples C2, C4, C5 and C7.

[0282] Furthermore, Table 2 confirms that i) the compositions of Examples 1 to 4 have superior copper film etching suppression performance compared to the compositions of Comparative Examples C2, C5 and C7, and ii) the compositions of Examples 1 to 5 have superior cobalt film etching suppression performance compared to the compositions of Comparative Examples C2, C4 and C7.

[0283] Depend on Figure 6A and 6BAs can be confirmed by Table 2, compared with the compositions of Comparative Examples C2, C4, C5 and C7, the compositions of Examples 1 to 5 have superior cleaning performance for residues generated during the deposition process and / or patterning process of metal-containing layers, and at the same time can more effectively suppress the etching of copper and cobalt films.

[0284] The composition exhibits improved and / or superior etch rate control and improved and / or superior cleaning performance without bubble formation, and therefore can be effectively used in various processing techniques, such as etching and cleaning processes, for a variety of metal-containing layers. Consequently, by using the composition to treat metal-containing layers, higher quality electronic devices can be manufactured.

[0285] It should be understood that the embodiments described herein are to be considered in a descriptive sense only and are not intended for limiting purposes. The descriptions of features or aspects within each embodiment should typically be considered applicable to other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the accompanying drawings, those skilled in the art will understand that various changes in form and detail may be made therein without departing from the spirit and scope defined by the appended claims.

Claims

1. A composition comprising: Oxidizing agent; Ammonium-containing compounds; and Etching control agent, wherein: The etching control agent comprises a compound represented by Formula 1. Formula 1 In Equation 1, L1 and L2 are each independently a single bond or an oxygen atom. R1 is hydrogen, C1-C 50 Alkyl, or C2-C 50 alkenyl, R2 and R3 are each independently C1-C 50 Alkyl or C2-C 50 alkenyl, and In R2, R3, and R1 when R1 is not hydrogen, the C1-C 50 Alkyl groups and the C2-C 50 At least one hydrogen atom in each of the alkenyl groups is optionally replaced by a halogen atom.

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 from about 1% to about 50% by weight relative to 100% by weight of the composition.

4. The composition according to claim 1, wherein the ammonium-containing compound in the composition comprises dihydrogen phosphate ([H₂PO₄]₂). - ), hydrogen phosphate ([HPO4)) 2- ), or phosphate ([PO4]) 3- ).

5. The composition according to claim 1, wherein the ammonium-containing compound comprises a compound represented by formula 11-1, a compound represented by formula 11-2, a compound represented by formula 11-3, 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 in, In equations 11-1 to 11-3, 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.

6. The composition according to claim 1, wherein the amount of the ammonium-containing compound is from about 0.01% to about 10% by weight relative to 100% by weight of the composition.

7. The composition according to claim 1, wherein, In Equation 1, L1 is oxygen and L2 is a single bond, or L1 and L2 are both oxygen.

8. The composition according to claim 1, wherein, In Formula 1, R1 is hydrogen or a C1-C5 alkyl group.

9. The composition according to claim 1, wherein, In Equation 1, R2 and R3 are each branched C3-C 50 alkyl.

10. The composition according to claim 1, wherein, The etching control agent further comprises an azole-containing compound, wherein the azole-containing compound comprises a pyrazole group, an imidazole group, a triazole group, or a tetraazole group.

11. The composition according to claim 1, wherein The amount of the etching control agent is about 0.001% to about 10% by weight relative to 100% by weight of the composition.

12. A method for processing a metal-containing layer, the method comprising: Prepare a metal-containing layer comprising a first region and a second region, wherein the material in the first region of the metal-containing layer is different from the material in the second region of the metal-containing layer; and The metal-containing layer is brought into contact with the composition according to any one of claims 1 to 11. The first region of the metal-containing layer and the second region of the metal-containing layer each independently comprise titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), copper (Cu), cobalt (Co), tungsten (W), ruthenium (Ru), molybdenum (Mo), zinc (Zn), hafnium (Hf), or any combination thereof.

13. The method of claim 12, wherein The first region of the metal-containing layer includes copper (Cu), cobalt (Co), tungsten (W), ruthenium (Ru), or any combination thereof, and The second region of the metal-containing layer includes titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), or any combination thereof.

14. The method of claim 12, wherein The second etch rate at which the composition etches the second region of the metal-containing layer is greater than the first etch rate at which the composition etches the first region of the metal-containing layer.

15. A method for manufacturing a semiconductor device, the method comprising: A mask pattern is formed by preparing a first insulating layer, a first conductive pattern in the first insulating layer, a second insulating layer on the first insulating layer, and an opening on the second insulating layer. An opening is formed in the second insulating layer by etching the second insulating layer using the opening to form a mask pattern; The opening forms a mask pattern and the exposed surface inside the opening contacts the composition according to any one of claims 1 to 11; as well as A conductive material is provided in the opening, the conductive material being configured to be electrically connected to the first conductive pattern.

16. The method according to claim 15, The first conductive pattern comprises copper (Cu), cobalt (Co), tungsten (W), ruthenium (Ru), or any combination thereof, and The opening forms a mask pattern comprising titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), or any combination thereof.

17. The method according to claim 15, The opening forming the mask pattern includes metal nitrides, metal oxynitrides, or any combination thereof.

18. The method according to claim 15, The opening forming the mask pattern includes titanium nitride, titanium oxynitride, or any combination thereof, The titanium nitride and the titanium oxynitride each optionally further comprise indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

19. The method according to claim 15, The first conductive pattern includes a first barrier layer pattern and a first fill layer on the first barrier layer pattern.

20. The method according to claim 15, During the formation of the opening, surface residue is formed on at least one of the surface on which the mask pattern of the opening is formed and on at least one of the exposed surfaces inside the opening. The opening forming mask pattern and the surface residue are removed by contacting the exposed surface inside the opening with the composition.

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