Etching composition, method for etching metal-containing film using same, and method for manufacturing semiconductor device using same

Abstract

Provided are an etching composition, a method of etching a metal-containing film using the same, and a method of manufacturing a semiconductor device using the same. The etching composition includes an oxidizing agent, an acid, and a selective etch inhibitor, where the oxidizing agent is metal-free, the selective etch inhibitor includes a copolymer comprising a first repeating unit and a second repeating unit, the first repeating unit being different from the second repeating unit, and the first repeating unit is a nitrogen-containing repeating unit.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is based on and claims the benefit of priority from Korean Patent Application No. 10-2023-0080674 filed on June 22, 2023 in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference. Technical Field

[0003] The present disclosure relates to an etching composition, a method of etching a metal-containing film using the same, and a method of manufacturing a semiconductor device using the same. Background Art

[0004] In order to meet the needs of customers for excellent performance and low cost, semiconductor devices may be required to have increased integration and improved reliability. As the integration of semiconductor devices increases, damage to components of semiconductor devices during the manufacturing process may have a greater impact on the reliability and electrical characteristics of semiconductor memory devices. In particular, during the semiconductor device manufacturing process, various etching processes may be performed on certain films (e.g., metal-containing films). In order to perform an effective etching process, there may be a continued need for an etching composition that can provide a high etching rate, excellent etching selectivity to adjacent films, no surface residues after etching, excellent storage stability, etc. Summary of the invention

[0005] Provided is an etching composition capable of improving productivity and efficiency of an etching process while having excellent etching selectivity for a metal-containing film as a film to be etched.

[0006] Additional 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 presented embodiments of the disclosure.

[0007] According to an embodiment of the present disclosure, the etching composition may include an oxidant, an acid, and a selective etching inhibitor. The oxidant may be metal-free, and the selective etching inhibitor may include a copolymer including a first repeating unit and a second repeating unit. The first repeating unit may be different from the second repeating unit, and the first repeating unit may be a nitrogen-containing repeating unit.

[0008] In some embodiments, the oxidizing agent may be hydrogen peroxide.

[0009] In some embodiments, the amount of the oxidizing agent may be in a range of 0.1 wt % to 50 wt % relative to 100 wt % of the etching composition.

[0010] In some embodiments, the acid may include at least one of phosphoric acid, hydrochloric acid, and chloric acid.

[0011] In some embodiments, the first repeating unit of the copolymer may include at least one of a repeating unit represented by the following Formula 1-1, a repeating unit represented by the following Formula 1-2, a repeating unit represented by the following Formula 1-3, and a repeating unit represented by the following Formula 1-4:

[0012]

[0013] Wherein A in Formulas 1-1 to 1-3 1 Can be *-C(R 16 )(R 17 )-*'、*-N(R 16 )-*', *-C(=O)-*', *-O-*', or *-S-*',

[0014] a1 in Formulas 1-1 to 1-3 may be an integer from 0 to 20, wherein when a1 is 2 or more and less than or equal to 20, at least two A 1 may be the same or different from each other,

[0015] b1 in Formulae 1-1 to 1-4 may be an integer from 0 to 10, wherein when b1 is 2 or more and less than or equal to 10, at least two *-C(R 14 )(R 15 )-*' may be the same or different from each other,

[0016] b2 in Formulas 1-3 and 1-4 may be an integer from 0 to 10, wherein when b2 is 2 or greater and less than or equal to 10, at least two *-C(R 12 )(R 13 )-*' may be the same or different from each other,

[0017] T in formulas 1-1 to 1-3 1 Can be *-N(Z 11 )(Z 12 )、*-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - , a group represented by the following formula AN, or a group represented by the following formula BN,

[0018]

[0019] Ring CY in Formulas 1-3, 1-4, AN and BN 1 To CY 4 Each independently can be C 2 -C 10 Cyclic groups,

[0020] c1 in Formulas 1-3, 1-4, AN and BN may be an integer from 0 to 10, wherein when c1 is 2 or greater and less than or equal to 10, at least two R 1 may be the same or different from each other,

[0021] T in formula 1-4 and AN 2 Can be *-N(Z 11 )-*' or *-[N(Z 11 )(Z 12 )] + [Z 14 ] - -*',

[0022] R 1 , R 11 To R 17 , and Z 11 To Z 13 Each independently can be:

[0023] Hydrogen, deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 1 、*-NH-C(=O)-Q 1 、*-C(=O)-OQ 1 、*-SO 2 -Q 1 、*-P(=O)-(Q 1 )(Q 2 )、*-N(Q 1 )(Q 2 )、*-[N(Q 1 )(Q 2 )(Q 3 )] + [Q 4 ] - , or *-(O-CH 2 CH 2 ) n1 -OH; or

[0024] Each unsubstituted or substituted C 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic groups, or C 1 -C 30 Heterocyclic groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q1 、*-NH-C(=O)-Q 1 、*-C(=O)-OQ 1 、*-SO 2 -Q 1 、*-P(=O)-(Q 1 )(Q 2 )、*-N(Q 11 )(Q 12 )、*-[N(Q 11 )(Q 12 )(Q 13 )] + [Q 14 ] - 、*-(O-CH 2 CH 2 ) n1 -OH, C 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic group, C 1 -C 30 Heterocyclic group, or any combination thereof,

[0025] n1 can be an integer from 1 to 20,

[0026] R 1 , R 11 To R 17 , and Z 11 To Z 13 At least two of the 2 -C 10 Cyclic groups,

[0027] Q 1 To Q 3 and Q 11 To Q 13 Each independently can be:

[0028] Hydrogen, deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH 2 、*-C(=O)-NH(CH 3 )、*-C(=O)-N(CH 3 ) 2 、*-NH-C(=O)-NH 2 、*-NH-C(=O)-NH(CH 3)、*-NH-C(=O)-N(CH 3 ) 2 、*-NH 2 、*-NH(CH 3 ), or *-N(CH 3 ) 2 ;or

[0029] Each C is unsubstituted or substituted as follows 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic groups, or C 1 -C 30 Heterocyclic groups: deuterium, -F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH 2 、*-C(=O)-NH(CH 3 )、*-C(=O)-N(CH 3 ) 2 、*-NH-C(=O)-NH 2 、*-NH-C(=O)-NH(CH 3 )、*-NH-C(=O)-N(CH 3 ) 2 、*-NH 2 、*-NH(CH 3 )、*-N(CH 3 ) 2 , C 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic group, C 1 -C 30 Heterocyclic group, or any combination thereof,

[0030] [Z 14 ] - , [Q 4 ] - and [Q 14 ] - may each be an anion, and

[0031] * and *' each represent a binding site with an adjacent atom.

[0032] In some embodiments, the first repeating unit may include a repeating unit represented by Formula 1-4, and the ring CY in Formula 1-4 2 It may be a saturated cyclic group having 4, 5, 6, or 7 carbon atoms.

[0033] In some embodiments, the first repeating unit may include a repeating unit represented by Formula 1-4, and the repeating unit represented by Formula 1-4 may be a repeating unit represented by one of the following Formulae 1-4(1) to 1-4(3):

[0034]

[0035] Wherein, in Formulas 1-4(1) to 1-4(3),

[0036] b1, b2, R 1 , R 12 To R 15 , and T 2 can be the same as described in this article,

[0037] c16 can be an integer from 0 to 6,

[0038] c18 can be an integer from 0 to 8, and

[0039] * and *' each represent a binding site with an adjacent atom.

[0040] In some embodiments, the second repeating unit of the copolymer may include at least one of a repeating unit obtained from (derived from) a sulfur dioxide-containing compound, a repeating unit obtained from an amide-containing compound, and a repeating unit obtained from a carboxylic acid-containing compound.

[0041] In some embodiments, the second repeating unit of the copolymer may include at least one of a repeating unit represented by the following Formula 2-1, a repeating unit represented by the following Formula 2-2, and a repeating unit represented by the following Formula 2-3:

[0042]

[0043] Among them, in formulas 2-1 to 2-3,

[0044] R 21 and R 22 Each independently can be:

[0045] Hydrogen, deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 21 、*-NH-C(=O)-Q 21 、*-C(=O)-OQ 21 、*-SO2 -Q 21 、*-P(=O)-(Q 21 )(Q 22 ), or *-N(Q 21 )(Q 22 );or

[0046] Each C is unsubstituted or substituted as follows 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic groups, or C 1 -C 30 Heterocyclic groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 21 、*-NH-C(=O)-Q 21 、*-C(=O)-OQ 21 、*-SO 2 -Q 21 、*-P(=O)-(Q 21 )(Q 22 )、*-N(Q 21 )(Q 22 ), C 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic group, C 1 -C 30 Heterocyclic group, or any combination thereof,

[0047] Q 21 and Q 22 Can be independently:

[0048] Hydrogen, deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH 2 、*-C(=O)-NH(CH 3 )、*-C(=O)-N(CH 3 ) 2 、*-NH-C(=O)-NH 2 、*-NH-C(=O)-NH(CH 3)、*-NH-C(=O)-N(CH 3 ) 2 、*-NH 2 、*-NH(CH 3 ), or *-N(CH 3 ) 2 ;or

[0049] Each C is unsubstituted or substituted as follows 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic groups, or C 1 -C 30 Heterocyclic groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH 2 、*-C(=O)-NH(CH 3 )、*-C(=O)-N(CH 3 ) 2 、*-NH-C(=O)-NH 2 、*-NH-C(=O)-NH(CH 3 )、*-NH-C(=O)-N(CH 3 ) 2 、*-NH 2 、*-NH(CH 3 )、*-N(CH 3 ) 2 , C 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic group, C 1 -C 30 Heterocyclic group, or any combination thereof, and

[0050] * and *' each represent a binding site with an adjacent atom.

[0051] In some embodiments, the copolymer may further include a third repeating unit in addition to the first repeating unit and the second repeating unit, and the third repeating unit may be different from each of the first repeating unit and the second repeating unit.

[0052] In some embodiments, the copolymer may have a weight average molecular weight of about 200 g / mol to about 100,000 g / mol.

[0053] In some embodiments, the selective etching inhibitor may further include an amine-containing compound, and the amine-containing compound may be different from the copolymer.

[0054] In some embodiments, the amine-containing compound may include an alkylamine, an alkanolamine, or any combination thereof.

[0055] In some embodiments, the amount of the selective etching inhibitor may be in a range of 0.001 wt % to 20 wt % relative to 100 wt % of the etching composition.

[0056] In some embodiments, the etching composition may have a pH of 1.0 to 3.0.

[0057] According to an embodiment of the present disclosure, a method of etching a metal-containing film may include preparing a substrate having a metal-containing film, and performing an etching process of the metal-containing film using any one of the above etching compositions to remove at least a portion of the metal-containing film.

[0058] In some embodiments, the metal-containing film may include indium (In), titanium (Ti), aluminum (Al), tungsten (W), lanthanum (La), scandium (Sc), gallium (Ga), zinc (Zn), hafnium (Hf), or any combination thereof.

[0059] In some embodiments, the metal-containing film may include a first region and a second region. The etching process of the metal-containing film using the etching composition may etch the first region at a first etching rate and etch the second region at a second etching rate. The second etching rate may be higher than the first etching rate. The etching process may include contacting at least a portion of the first region with the etching composition, and contacting at least a portion of the second region with the etching composition.

[0060] According to an embodiment of the present disclosure, a method for manufacturing a semiconductor device may include: preparing a substrate having a metal-containing film, performing an etching process of the metal-containing film using any one of the above-mentioned etching compositions to remove at least a portion of the metal-containing film, and performing one or more subsequent manufacturing processes to thereby complete the formation of the semiconductor device. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] The above and other aspects, features and advantages of some embodiments of the present disclosure will become more apparent from the following description in conjunction with the accompanying drawings, in which:

[0062] Figure 1A flowchart of an embodiment of a method for manufacturing a semiconductor device; and

[0063] Figure 2 and 3 is a schematic diagram for explaining an embodiment of a method for etching a metal-containing film. DETAILED DESCRIPTION

[0064] 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 regard, the present embodiment may have different forms and should not be construed as being limited to the description set forth herein. Therefore, the following only describes the embodiment to illustrate aspects by reference to the accompanying drawings. As used herein, the term "and / or" includes any and all combinations of one or more of the related listed items. When before or after the list of elements, statements such as "at least one (kind) of ... " modify the entire list of elements, and do not modify the individual elements of the list. For example, "at least one (kind) of A, B and C" and similar language (e.g., "at least one (kind) selected from A, B and 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.

[0065] When the term "about" or "substantially" is used in conjunction with a numerical value in this specification, it is intended that the relevant numerical value includes a manufacturing or operating tolerance (e.g., ±10%) around the stated numerical value. In addition, when the words "substantially" and "substantially" are used in conjunction with a geometric shape, it is intended that the accuracy of the geometric shape is not required, but that the tolerance for the shape is within the scope of the present disclosure. In addition, regardless of whether a numerical value or shape is modified as "about" or "substantially", it will be understood that these values ​​and shapes should be interpreted as including manufacturing or operating tolerances (e.g., ±10%) around the stated numerical value or shape. When a range is specified, the range includes all values ​​therebetween, such as increments of 0.1%.

[0066] Film to be etched

[0067] The film to be etched may include a metal-containing film.

[0068] Therefore, the etching composition can be used in an etching process and / or a chemical mechanical polishing (CMP) process for the metal-containing film.

[0069] The metal included in the metal-containing film 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.), lanthanide metals (e.g., lanthanum (La), europium (Eu), terbium (Tb), ytterbium (Yb), etc.), transition metals (e.g., scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), 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.), late transition metals (such as aluminum (Al), gallium (Ga), indium (In), thallium (Tl), tin (Sn), bismuth (Bi), etc.), or any combination thereof.

[0070] According to an embodiment, the metal-containing film may include In, Ti, Al, Cu, W, Co, La, Sc, Ga, Zn, Hf, or any combination thereof.

[0071] According to an embodiment, the metal-containing film may include In, Ti, Al, W, La, Sc, Ga, Zn, Hf, or any combination thereof.

[0072] For example, the metal-containing film may include aluminum, titanium, lanthanum, tungsten, or any combination thereof.

[0073] In an embodiment, the metal-containing film may include titanium.

[0074] In an embodiment, the metal-containing film may include titanium and aluminum.

[0075] In an embodiment, the metal-containing film may include tungsten.

[0076] The metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.

[0077] The metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof, and the metal included in each of the metal, the metal nitride, the metal oxide, and the metal oxynitride may include In, Ti, Al, La, Sc, Ga, Zn, Hf, or any combination thereof.

[0078] The metal-containing film may include a metal nitride. The metal included in the metal nitride may include indium, titanium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof.

[0079] For example, the metal-containing film may include a metal, such as tungsten.

[0080] In an embodiment, the metal-containing film may include titanium nitride. The titanium nitride may further include indium, aluminum, lanthanum, scandium, gallium, hafnium, zinc, or any combination thereof. In an embodiment, the metal-containing film may include titanium nitride (TiN), further including titanium nitride of aluminum (e.g., titanium / aluminum nitride or TiAlN), further including titanium nitride of lanthanum, etc.

[0081] In an embodiment, the metal-containing film may include a metal oxide. The metal included in the metal oxide may include titanium, aluminum, lanthanum, scandium, gallium, hafnium, or any combination thereof. For example, the metal-containing film may include aluminum oxide (e.g., Al 2 O 3 ), indium gallium zinc oxide (IGZO), etc.

[0082] In an embodiment, the metal-containing film may include a metal and a metal nitride.

[0083] In an embodiment, in addition to metals, the metal-containing film may further include: metalloids (such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), etc.), non-metals (such as nitrogen (N), phosphorus (P), oxygen (O), sulfur (S), selenium (Se), etc.), or any combination thereof.

[0084] For example, the metal-containing film may further include silicon oxide.

[0085] The metal-containing film may have a single-layer structure composed of one or more types of materials (or including one or more types of materials), or may have a multilayer structure or a patterned structure including different materials. For example, the metal-containing film may have: i) a single-layer structure composed of titanium nitride (or including titanium nitride), ii) a double-layer structure or a patterned structure including: a first layer composed of titanium nitride (or including titanium nitride); and a second layer composed of titanium nitride further including aluminum (or including titanium nitride further including aluminum), iii) a double-layer structure or a patterned structure including: a first layer composed of titanium nitride (or including titanium nitride); and a second layer composed of aluminum oxide (or including aluminum oxide); and iv) a double-layer structure or a patterned structure including: a first layer composed of titanium nitride (or including titanium nitride); and a second layer composed of tungsten (or including tungsten), and so on.

[0086] According to an embodiment, the metal-containing film may include a first region and a second region, and a second etching rate at which the etching composition etches the second region may be higher than a first etching rate at which the etching composition etches the first region. During an etching process and / or a polishing process of the metal-containing film, at least a portion of the first region and at least a portion of the second region may be in contact with the etching composition, and since the second etching rate is higher than the first etching rate, the second region may be etched faster than the first region.

[0087] For example, the first region may include at least one of a metal, a metal oxide (eg, aluminum oxide), and a silicon oxide.

[0088] According to an embodiment, the first region may include tungsten.

[0089] In an embodiment, the second region may include a metal nitride.

[0090] In an embodiment, the second region may include: i) titanium nitride, ii) titanium nitride further including indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof.

[0091] In an embodiment, the first region and the second region each may include: i) titanium nitride, ii) titanium nitride further including indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof.

[0092] In an embodiment, the first region may include aluminum and the second region may be free of aluminum.

[0093] In an embodiment, the first region may include titanium nitride further including aluminum (eg, titanium / aluminum nitride or TiAlN), and the second region may include titanium nitride (TiN).

[0094] In an embodiment, the first region may include a titanium nitride film further including aluminum (eg, a titanium / aluminum nitride film or a TiAlN film), and the second region may include a titanium nitride (TiN) film.

[0095] In an embodiment, the first region may be a titanium nitride film further including aluminum (eg, a titanium / aluminum nitride film or a TiAlN film), and the second region may be a titanium nitride (TiN) film.

[0096] In an embodiment, the first region may include tungsten and the second region may be tungsten-free.

[0097] In an embodiment, the first region may include tungsten, and the second region may include titanium nitride (TiN).

[0098] In an embodiment, the first region may include a tungsten film, and the second region may include a titanium nitride (TiN) film.

[0099] In an embodiment, the first region may be a tungsten film, and the second region may be a titanium nitride (TiN) film.

[0100] The expression “etching a layer” as used herein may mean removing at least some of the material constituting the film.

[0101] Etching composition

[0102] The etching composition may include an oxidizing agent, an acid, and a selective etch inhibitor.

[0103] The etching composition can be used in an etching process and / or a chemical mechanical polishing (CMP) process of a film to be etched (eg, a metal-containing film) as described herein.

[0104] The etching composition may further include water.

[0105] According to an embodiment, the etching composition may consist of an oxidizing agent, an acid, a selective etching inhibitor, and water.

[0106] According to an embodiment, the etching composition may be free of copper ions, nitric acid, sulfonic acid, fluorine compounds (eg, hydrofluoric acid, ammonium fluoride, ammonium hydrogen fluoride, hexafluorosilicic acid, ammonium silicon hexafluoride, ammonium tetrafluoroborate, etc.), and phosphine-based compounds.

[0107] Oxidants

[0108] The oxidizing agent is used to etch the metal-containing film and does not contain metal (eg, metal ions, etc.).

[0109] For example, the oxidizing agent may include at least one of hydrogen peroxide, nitric acid, and ammonium sulfate.

[0110] According to an embodiment, the oxidizing agent may be hydrogen peroxide.

[0111] According to an embodiment, the amount (weight) of the oxidizing agent, relative to 100 wt % of the etching composition, may be, for example, in the following ranges: about 0.001 wt % to about 50 wt %, about 0.001 wt % to about 40 wt %, about 0.001 wt % to about 30 wt %, about 0.001 wt % to about 20 wt %, about 0.001 wt % to about 10 wt %, about 0.01 wt % to about 50 wt %, about 0.01 wt % to about 40 wt %, about 0.01 wt % to about 30 wt %, about 0.01 wt % to about 20 wt %, about 0.01 wt % to about 10 wt %, about 0.1 wt % to about 50 wt %, about 0.1 wt % to about 40 wt %, about 0.1 wt % to about 30 wt %, about 0.1 wt % to about 20 wt %, about 0.1 wt % to about 10 wt %, about 0.5 wt %. % to about 50 wt %, about 0.5 wt % to about 40 wt %, about 0.5 wt % to about 30 wt %, about 0.5 wt % to about 20 wt %, about 0.5 wt % to about 10 wt %, about 1.0 wt % to about 50 wt %, about 1.0 wt % to about 40 wt %, about 1.0 wt % to about 30 wt %, about 1.0 wt % to about 20 wt %, about 1.0 wt % to about 10 wt %, about 3.0 wt % to about 50 wt %, about 3.0 wt % to about 40 wt %, about 3.0 wt % to about 30 wt %, about 3.0 wt % to about 20 wt %, about 3.0 wt % to about 10 wt %, about 5.0 wt % to about 50 wt %, about 5.0 wt % to about 40 wt %, about 5.0 wt % to about 30 wt %, about 5.0 wt % to about 20 wt %, or about 5.0 wt % to about 10 wt %.

[0112] acid

[0113] The acid may be used together with the oxidizing agent to etch the metal-containing film.

[0114] The acid may include a phosphorus-based inorganic acid, a chlorine-based inorganic acid, a fluorine-based inorganic acid, or any combination thereof.

[0115] For example, the acid may be free of at least one of nitric acid and sulfuric acid.

[0116] For example, the acid may include at least one of a phosphorus-based inorganic acid and a chlorine-based inorganic acid.

[0117] According to an embodiment, the acid may include at least one of phosphoric acid, hydrochloric acid, and chloric acid.

[0118] The amount (by weight) of the acid, relative to 100 wt % of the etching composition, may be, for example, in the following ranges: about 0.01 wt % to about 90 wt %, about 0.1 wt % to about 90 wt %, about 1.0 wt % to about 90 wt %, about 10 wt % to about 90 wt %, about 20 wt % to about 90 wt %, about 30 wt % to about 90 wt %, about 40 wt % to about 90 wt %, about 50 wt % to about 90 wt %, about 0.01 wt % to about 80 wt %, about 0.1 wt % to about 8 ... 80 wt %, about 10 wt % to about 80 wt %, about 20 wt % to about 80 wt %, about 30 wt % to about 80 wt %, about 40 wt % to about 80 wt %, about 50 wt % to about 80 wt %, about 0.01 wt % to about 70 wt %, about 0.1 wt % to about 70 wt %, about 1.0 wt % to about 70 wt %, about 10 wt % to about 70 wt %, about 20 wt % to about 70 wt %, about 30 wt % to about 70 wt %, about 40 wt % to about 70 wt %, or about 50 wt % to about 70 wt %.

[0119] According to an embodiment, the acid may be an organic acid, such as acetic acid, tartaric acid, benzoic acid, and the like.

[0120] Selective Etch Inhibitors

[0121] The selective etching inhibitor may be used to control an etching rate or the like by interacting with metal atoms (eg, titanium atoms) in a metal-containing film as a film to be etched.

[0122] The selective etching inhibitor may include a copolymer including a first repeating unit and a second repeating unit. The copolymer may be a water-soluble copolymer. The number of different repeating units included in the copolymer may be 2 or more.

[0123] The first repeating unit may be different from the second repeating unit.

[0124] The first repeating unit may be a nitrogen-containing repeating unit.

[0125] According to an embodiment, the first repeating unit may be a repeating unit derived from a nitrogen-containing ethylene-based unsaturated compound. The nitrogen-containing ethylene-based unsaturated compound may include dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkyl acrylamide, dialkylaminoalkyl methacrylamide, allylamine, diallylamine, dimethylallylamine, methyldiallylamine, 2-vinylpyridine, 4-vinylpyridine, N', N'-dimethylaminoethyl-N, N-dimethylammonium-N-propyl methacrylate chloride (N', N'-dimethylaminoethyl-N, N-dimethyl-N-methacryloyloxypropylammonium chloride), or any combination thereof. As used herein, the term "alkyl" may refer to C 1 -C 50 alkyl.

[0126] According to an embodiment, the first repeating unit may include at least one of a repeating unit represented by the following Formula 1-1, a repeating unit represented by the following Formula 1-2, a repeating unit represented by the following Formula 1-3, and a repeating unit represented by the following Formula 1-4:

[0127]

[0128] A in Formulas 1-1 to 1-3 1 Can be *-C(R 16 )(R 17 )-*'、*-N(R 16 )-*', *-C(=O)-*', *-O-*', or *-S-*'.

[0129] a1 in Formulas 1-1 to 1-3 may be an integer from 0 to 20, wherein when a1 is 2 or more and less than or equal to 20, at least two A 1 They may be the same or different from each other. When a1 is 0, *-(A 1 ) a1 -*' can be a single bond.

[0130] According to an embodiment, a1 may be 0.

[0131] According to the implementation, a1 may not be 0.

[0132] According to an embodiment, a1 may be an integer from 0 to 10.

[0133] According to an embodiment, a1 may be an integer from 1 to 5.

[0134] b1 in Formulae 1-1 to 1-4 may be an integer from 0 to 10, wherein when b1 is 2 or more and less than or equal to 10, at least two *-C(R 14 )(R 15)-*' may be the same or different from each other. When b1 is 0, *-C(R 14 )(R 15 )-*' may be a single bond.

[0135] b2 in Formulas 1-3 to 1-4 may be an integer from 0 to 10, wherein when b2 is 2 or more and less than or equal to 10, at least two *-C(R 12 )(R 13 )-*' may be the same or different from each other. When b2 is 0, *-C(R 12 )(R 13 )-*' may be a single bond.

[0136] According to an embodiment, b1 may be an integer from 1 to 5.

[0137] According to an embodiment, b2 may be an integer from 0 to 2.

[0138] According to an embodiment, b1 and b2 in Formulae 1-3 and 1-4 may each be 1.

[0139] T in formulas 1-1 to 1-3 1 Can be *-N(Z 11 )(Z 12 )、*-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - , a group represented by the following formula AN, or a group represented by the following formula BN:

[0140]

[0141] Ring CY in Formulas 1-3, 1-4, AN and BN 1 To CY 4 Each independently can be C 2 -C 10 Cyclic group.

[0142] According to an embodiment, T in Formulas 1-1 to 1-3 1 Can be *-N(Z 11 )(Z 12 ) or *-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - , and Z 11 To Z 13 Each may be hydrogen.

[0143] According to an embodiment, T in Formulas 1-1 to 1-3 1 Can be *-N(Z 11 )(Z 12 ) or *-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - , and Z 11 Can be hydrogen and Z 12 It may not be hydrogen.

[0144] According to an embodiment, T in Formulas 1-1 to 1-3 1 Can be *-N(Z 11 )(Z 12 ) or *-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - , and Z 11 and Z 12 Each may not be hydrogen.

[0145] According to an embodiment, T in Formulas 1-1 to 1-3 1 Can be *-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - , and Z 11 To Z 13 Each may not be hydrogen.

[0146] According to an embodiment, T in Formulas 1-1 to 1-3 1 may be a group represented by the formula AN, and T of the formula AN 2 Z 11 and Z 12 It may be hydrogen.

[0147] According to an embodiment, T in Formulas 1-1 to 1-3 1 may be a group represented by the formula AN, and T of the formula AN 2 Z 11 It may not be hydrogen.

[0148] According to an embodiment, T in Formulas 1-1 to 1-3 1 may be a group represented by the formula AN, and T of the formula AN 2 Can be *-[N(Z 11 )(Z 12 )] +[Z 14 ] - -*', where Z 11 and Z 12 Each may not be hydrogen.

[0149] According to an embodiment, in T of Formula 1-4, 2 In, Z 11 and Z 12 Each may be hydrogen.

[0150] According to an embodiment, in T of Formula 1-4, 2 In, Z 11 may not be hydrogen, and Z 12 It may be hydrogen.

[0151] According to an embodiment, T of Formula 1-4 2 Can be *-[N(Z 11 )(Z 12 )] + [Z 14 ] - -*', and Z 11 and Z 12 Each may not be hydrogen.

[0152] In formulas 1-3, 1-4, AN and BN, c1 refers to R 1 The number of R is an integer from 0 to 10. When c1 is 2 or more and less than or equal to 10, at least two R 1 Can be the same as or different from each other.

[0153] In equations 1-4 and AN, T 2 Can be *-N(Z 11 )-*' or *-[N(Z 11 )(Z 12 )] + [Z 14 ] - -*'. About Z 11 , Z 12 and Z 14 See the description provided herein for details.

[0154] According to an embodiment, CY in Formula 1-3 1 It may be a cyclopropane group, a cyclobutane group, a cyclopentane group, a cyclohexane group, a cycloheptane group, a cyclooctane group, an oxirane group, an oxetane group, a tetrahydrofuran group, or a tetrahydropyran group.

[0155] According to an embodiment, the ring CY in formula 1-4 2 It may be a saturated cyclic group having 4, 5, 6 or 7 carbon atoms.

[0156] According to an embodiment, in Formula AN,

[0157] i)T 2 Can be *-N(Z 11 )-*', and the ring CY 3 may be a pyrrole group, an imidazole group, a pyrazole group, an aziridine group, an azetidine group, a pyrrolidine group, or a piperidine group, or

[0158] ii) T 2 Can be *-[N(Z 11 )(Z 12 )] + [Z 14 ] - -*', and the ring CY 3 It may be a saturated cyclic group having 4, 5, 6 or 7 carbon atoms.

[0159] According to an embodiment, ring CY in formula BN 4 It may be a pyrrole group, an imidazole group, a pyrazole group, an aziridine group, an azetidine group, a pyrrolidine group, or a piperidine group.

[0160] R 1 , R 11 To R 17 , and Z 11 To Z 13 Each independently can be:

[0161] Hydrogen, deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 1 、*-NH-C(=O)-Q 1 、*-C(=O)-OQ 1 、*-SO 2 -Q 1 、*-P(=O)-(Q 1 )(Q 2 )、*-N(Q 1 )(Q 2 )、*-[N(Q 1 )(Q 2 )(Q 3 )] + [Q 4 ] - , or *-(O-CH 2 CH 2 ) n1 -OH; or

[0162] Each C is unsubstituted or substituted as follows 1 -C 30 Alkyl, C 1-C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic groups, or C 1 -C 30 Heterocyclic groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 1 、*-NH-C(=O)-Q 1 、*-C(=O)-OQ 1 、*-SO 2 -Q 1 、*-P(=O)-(Q 1 )(Q 2 )、*-N(Q 11 )(Q 12 )、*-[N(Q 11 )(Q 12 )(Q 13 )] + [Q 14 ] - 、*-(O-CH 2 CH 2 ) n1 -OH, C 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic group, C 1 -C 30 A heterocyclic group, or any combination thereof.

[0163] For example, R 1 , R 11 To R 17 , and Z 11 To Z 13 Each independently can be:

[0164] Hydrogen, deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 1 、*-NH-C(=O)-Q 1 、*-C(=O)-OQ 1 、*-SO 2 -Q 1 、*-P(=O)-(Q 1 )(Q 2 )、*-N(Q 1 )(Q2 )、*-[N(Q 1 )(Q 2 )(Q 3 )] + [Q 4 ] - , or *-(O-CH 2 CH 2 ) n1 -OH; or

[0165] C is unsubstituted or substituted as follows 1 -C 10 Alkyl: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 1 、*-NH-C(=O)-Q 1 、*-C(=O)-OQ 1 、*-SO 2 -Q 1 、*-P(=O)-(Q 1 )(Q 2 )、*-N(Q 11 )(Q 12 )、*-[N(Q 11 )(Q 12 )(Q 13 )] + [Q 14 ] - 、*-(O-CH 2 CH 2 ) n1 -OH, C 1 -C 10 alkyl, or any combination thereof.

[0166] n1 may be an integer from 1 to 20.

[0167] R 1 , R 11 To R 17 , and Z 11 To Z 13 At least two of the 2 -C 10 Cyclic group.

[0168] Q 1 To Q 3 and Q 11 To Q 13 Each independently can be:

[0169] Hydrogen, deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH 2 、*-C(=O)-NH(CH 3 )、*-C(=O)-N(CH 3 ) 2 、*-NH-C(=O)-NH 2 、*-NH-C(=O)-NH(CH 3 )、*-NH-C(=O)-N(CH 3 ) 2 、*-NH 2 、*-NH(CH 3 ), or *-N(CH 3 ) 2 ;or

[0170] Each C is unsubstituted or substituted as follows 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic groups, or C 1 -C 30 Heterocyclic groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH 2 、*-C(=O)-NH(CH 3 )、*-C(=O)-N(CH 3 ) 2 、*-NH-C(=O)-NH 2 、*-NH-C(=O)-NH(CH 3 )、*-NH-C(=O)-N(CH 3 ) 2 、*-NH 2 、*-NH(CH 3 )、*-N(CH 3 ) 2 , C 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic group, C 1 -C30 A heterocyclic group, or any combination thereof.

[0171] The C 3 -C 30 The carbocyclic group may be, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, and the like.

[0172] The C 1 -C 30 The heterocyclic group may be, for example, an oxirane group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, a pyridinyl group, a pyrimidinyl group, or the like.

[0173] [Z 14 ] - , [Q 4 ] - and [Q 14 ] - Each may be an anion.

[0174] For example, [Z 14 ] - , [Q 4 ] - and [Q 14 ] - Each independently may be a hydroxide ([OH] - ), borate ([B(OH) 4 ] - ), fluoride ([F] - ), chloride ([Cl] - ), bromide ([Br] - ), iodine ([I] - ), hydrogen sulfate ([HSO 4 ] - ), nitrate ([NO 3 ] - ), formate ([HCOO] - ), acetate ([CH 3 COO] - ), dihydrogen phosphate ([H 2 PO 4 ] - ), alkyl sulfate (e.g., ethyl sulfate ([C 2 H 5 SO 4 ] - )), or aminosulfonate ([NH 2 SO 3 ] - ).

[0175] In the specification, * and *' each represent a binding site with an adjacent atom unless otherwise defined.

[0176] According to an embodiment, the repeating unit represented by Formula 1-3 may be a repeating unit represented by one of Formulas 1-3(1) to 1-3(8):

[0177]

[0178] Wherein, in Formulas 1-3(1) to 1-3(8),

[0179] A 1 、a1、b1、b2、T 1 , R 1 , and R 12 To R 15 each being the same as described herein,

[0180] C11 can be 0 or 1.

[0181] C13 can be an integer from 0 to 3,

[0182] C15 can be an integer from 0 to 5,

[0183] C17 can be an integer from 0 to 7,

[0184] C19 may be an integer from 0 to 9, and

[0185] * and *' each represent a binding site with an adjacent atom.

[0186] According to an embodiment, the repeating unit represented by Formula 1-4 may be a repeating unit represented by one of the following Formulae 1-4(1) to 1-4(3):

[0187]

[0188] Wherein, in Formulas 1-4(1) to 1-4(3),

[0189] b1, b2, R 1 , R 12 To R 15 , and T 2 each being the same as described herein,

[0190] C16 can be an integer from 0 to 6,

[0191] C18 may be an integer from 0 to 8, and

[0192] * and *' each represent a binding site with an adjacent atom.

[0193] According to an embodiment, the group represented by formula AN may be a group represented by one of the following formulae AN(1) to AN(12):

[0194]

[0195] Wherein, in formulas AN(1) to AN(12),

[0196] R 1 and T 2 each being the same as described herein,

[0197] C12 can be an integer from 0 to 2,

[0198] C13 can be an integer from 0 to 3,

[0199] C16 can be an integer from 0 to 6,

[0200] C18 may be an integer from 0 to 8, and

[0201] * and *' each represent a binding site with an adjacent atom.

[0202] According to an embodiment, the group represented by formula BN may be a group represented by one of the following formulae BN(1) to BN(7):

[0203]

[0204] Wherein, in formulas BN(1) to BN(7),

[0205] R 1 Same as described in this article,

[0206] C13 can be an integer from 0 to 3,

[0207] C14 can be an integer from 0 to 4,

[0208] C16 can be an integer from 0 to 6,

[0209] C18 can be an integer from 0 to 8,

[0210] C20 may be an integer from 0 to 10, and

[0211] * indicates the binding site with the adjacent atom

[0212] The second repeating unit of the copolymer may include at least one of a repeating unit derived from a compound containing sulfur dioxide, a repeating unit derived from an amide-containing compound, and a repeating unit derived from a carboxylic acid-containing compound. For example, the amide-containing compound may include acrylamide (CH 2 =CHC(O)NH 2 ), methacrylamide (CH 2 =C(CH 3 )C(O)NH 2), diacetone acrylamide, N,N-dimethyl acrylamide, or any combination thereof. In addition, the carboxylic acid-containing compound may include acrylic acid or acrylic acid esters derived from alcohols having 1 to 30 carbon atoms, methacrylic acid or methacrylic acid esters derived from alcohols having 1 to 30 carbon atoms, unsaturated dicarboxylic acids having 1 to 30 carbon atoms (e.g., maleic acid), or any combination thereof.

[0213] According to an embodiment, the second repeating unit may include at least one of a repeating unit represented by the following Formula 2-1, a repeating unit represented by the following Formula 2-2, and a repeating unit represented by the following Formula 2-3:

[0214]

[0215] Among them, in formulas 2-1 to 2-3,

[0216] R 21 and R 22 Each independently can be:

[0217] Hydrogen, deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 21 、*-NH-C(=O)-Q 21 、*-C(=O)-OQ 21 、*-SO 2 -Q 21 、*-P(=O)-(Q 21 )(Q 22 ), or *-N(Q 21 )(Q 22 );or

[0218] Each C is unsubstituted or substituted as follows 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic groups, or C 1 -C 30 Heterocyclic groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 21 、*-NH-C(=O)-Q 21 、*-C(=O)-OQ 21 、*-SO 2 -Q 21 、*-P(=O)-(Q 21 )(Q 22 )、*-N(Q21 )(Q 22 ), C 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic group, C 1 -C 30 Heterocyclic group, or any combination thereof,

[0219] Q 21 and Q 22 Each independently can be:

[0220] Hydrogen, deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH 2 、*-C(=O)-NH(CH 3 )、*-C(=O)-N(CH 3 ) 2 、*-NH-C(=O)-NH 2 、*-NH-C(=O)-NH(CH 3 )、*-NH-C(=O)-N(CH 3 ) 2 、*-NH 2 、*-NH(CH 3 ), or *-N(CH 3 ) 2 ;or

[0221] Each C is unsubstituted or substituted as follows 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic groups, or C 1 -C 30 Heterocyclic groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH 2 、*-C(=O)-NH(CH 3 )、*-C(=O)-N(CH 3 ) 2 、*-NH-C(=O)-NH 2、*-NH-C(=O)-NH(CH 3 )、*-NH-C(=O)-N(CH 3 ) 2 、*-NH 2 、*-NH(CH 3 )、*-N(CH 3 ) 2 , C 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic group, C 1 -C 30 Heterocyclic group, or any combination thereof, and

[0222] * and *' each represent a binding site with an adjacent atom.

[0223] For example, R 21 and R 22 Each independently can be:

[0224] Hydrogen, deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 21 、*-NH-C(=O)-Q 21 、*-C(=O)-OQ 21 、*-SO 2 -Q 21 、*-P(=O)-(Q 21 )(Q 22 ), or *-N(Q 21 )(Q 22 );or

[0225] C is unsubstituted or substituted as follows 1 -C 10 Alkyl: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 21 、*-NH-C(=O)-Q 21 、*-C(=O)-OQ 21 、*-SO 2 -Q 21 、*-P(=O)-(Q 21 )(Q 22 )、*-N(Q 21 )(Q 22 ), C 1 -C 10 alkyl, or any combination thereof.

[0226] For example, Q 21 and Q 22 Each independently can be:

[0227] Hydrogen, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH 2 、*-C(=O)-NH(CH 3 )、*-C(=O)-N(CH 3 ) 2 、*-NH-C(=O)-NH 2 、*-NH-C(=O)-NH(CH 3 )、*-NH-C(=O)-N(CH 3 ) 2 、*-NH 2 、*-NH(CH 3 ), or *-N(CH 3 ) 2 ;or

[0228] C is unsubstituted or substituted as follows 1 -C 10 Alkyl: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH 2 、*-C(=O)-NH(CH 3 )、*-C(=O)-N(CH 3 ) 2 、*-NH-C(=O)-NH 2 、*-NH-C(=O)-NH(CH 3 )、*-NH-C(=O)-N(CH 3 ) 2 、*-NH 2 、*-NH(CH 3 )、*-N(CH 3 ) 2 , C 1 -C 10 alkyl, or any combination thereof.

[0229] The molar ratio of the first repeating unit to the second repeating unit in the copolymer may range from about 1:99 to about 99:1, about 10:90 to about 90:10, about 20:80 to about 80:20, about 30:70 to about 70:30, or about 40:60 to about 60:40.

[0230] According to an embodiment, the copolymer may further include a third repeating unit, and the third repeating unit may be different from each of the first repeating unit and the second repeating unit.

[0231] For example, the third repeating unit may include at least one of a repeating unit derived from a compound containing sulfur dioxide, a repeating unit derived from a compound containing amides, and a repeating unit derived from a compound containing carboxylic acid. The details of the amide-containing compound and the carboxylic acid-containing compound may refer to the description provided herein.

[0232] In an embodiment, the third repeating unit may include at least one of a repeating unit represented by the above Formula 2-1, a repeating unit represented by the above Formula 2-2, and a repeating unit represented by the above Formula 2-3.

[0233] The copolymer may be an alternating copolymer, a block copolymer, a random copolymer, or a graft copolymer.

[0234] The copolymer may have a weight average molecular weight of about 200 g / mol to about 100,000 g / mol.

[0235] According to an embodiment, the copolymer may be at least one of the following: diallyldimethyl-ammonium chloride sulfur dioxide copolymer, diallylamine sulfur dioxide copolymer, diallylamine hydrochloride sulfur dioxide copolymer, diallylmethylethyl-ethylammonium sulfate sulfur dioxide copolymer, diallylamine acetate sulfur dioxide copolymer, methyldiallylamine hydrochloride sulfur dioxide copolymer, diallylamine acrylamide copolymer, diallylamine hydrochloride acrylamide copolymer, diallyldimethyl-ammonium chloride acrylamide copolymer, diallylamine maleic acid copolymer, diallylamine hydrochloride maleic acid copolymer, diallylamine amidesulfate maleic acid copolymer (diallylamine amidesulfate maleic acid copolymer) copolymer) (or diallylamine sulfamate maleic acid copolymer), methyldiallylamine maleic acid copolymer, diallylmethylethyl-ethylammonium sulfate maleic acid copolymer, diallyldimethylammonium chloride maleic acid copolymer, diallylamine maleic acid sulfur dioxide copolymer, diallyldimethylammonium chloride maleic acid sulfur dioxide copolymer, and allylamine maleic acid copolymer.

[0236] According to an embodiment, the copolymer may be at least one of the following polymers 1 to 18:

[0237]

[0238]

[0239] Among them, in polymers 1 to 18,

[0240] n, o and p can each independently be selected from 1 to 10,000, and

[0241] * and *' each represent a binding site with an adjacent atom.

[0242] In Polymers 1 to 18, n, o, and p each independently may be an integer of 1 to 10,000.

[0243] Polymers 1 to 18 can have a weight average molecular weight within the ranges described herein.

[0244] The etching composition including the copolymer as described above can improve the productivity and efficiency of the etching process while having excellent selectivity to metal-containing films.

[0245] The selective etching inhibitor may further include an amine-containing compound different from the copolymer. By further including the amine-containing compound, the etching rate of the metal-containing film and the adjustment of its etching selectivity may be effectively controlled.

[0246] According to an embodiment, the amine-containing compound may include an alkylamine, an alkanolamine, or any combination thereof.

[0247] According to an embodiment, the amine-containing compound may include a monoalkylamine (eg, monobutylamine), a monoalkanolamine (eg, ethanolamine), or any combination thereof.

[0248] According to an embodiment, the amine-containing compound may include a compound represented by the following Formula 5:

[0249] Formula 5

[0250] N(Q 51 )(Q 52 )(Q 53 )

[0251] Among them, in formula 5, Q 51 To Q 53 Each independently can be:

[0252] Hydrogen, deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH 2 、*-C(=O)-NH(CH 3 )、*-C(=O)-N(CH 3 ) 2 、*-NH-C(=O)-NH 2 、*-NH-C(=O)-NH(CH 3 )、*-NH-C(=O)-N(CH 3 )2 、*-NH 2 、*-NH(CH 3 ), or *-N(CH 3 ) 2 ;or

[0253] Each C is unsubstituted or substituted as follows 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic groups, or C 1 -C 30 Heterocyclic groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH 2 、*-C(=O)-NH(CH 3 )、*-C(=O)-N(CH 3 ) 2 、*-NH-C(=O)-NH 2 、*-NH-C(=O)-NH(CH 3 )、*-NH-C(=O)-N(CH 3 ) 2 、*-NH 2 、*-NH(CH 3 )、*-N(CH 3 ) 2 , C 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 2 -C 30 Alkenyl, C 3 -C 30 Carbocyclic group, C 1 -C 30 Heterocyclic group, or any combination thereof,

[0254] And Q 51 To Q 53 At least one of may not be hydrogen.

[0255] For example, in Equation 5, Q 51 and Q 52 may each be hydrogen, and Q 53 Can be: C 1 -C 20 Alkyl; or C substituted by deuterium, *-F, *-OH, or any combination thereof1 -C 20 alkyl.

[0256] When the selective etching inhibitor further includes an amine-containing compound, a weight ratio of the copolymer to the amine-containing compound may be in a range of about 100:1 to about 1:100.

[0257] The amount (weight) of the selective etching inhibitor relative to 100 wt % of the etching composition, based on the solids of the selective etching inhibitor, may be, for example, in the following ranges: about 0.001 wt % to about 20 wt %, about 0.001 wt % to about 15 wt %, about 0.001 wt % to about 10 wt %, about 0.001 wt % to about 7 wt %, about 0.001 wt % to about 5 wt %, about 0.001 wt % to about 4 wt %, about 0.001 wt % to about 3 wt %, about 0.001 wt % to about 2 wt %, about 0.001 wt % to about 1 wt %, about 0.001 wt % to about 0.5 wt %, about 0.001 wt % to about 10 wt %, about 0.001 wt % to about 1 ...5 wt %, about 0.001 wt % to about 15 wt %, about % to about 0.3 wt %, about 0.005 wt % to about 20 wt %, about 0.005 wt % to about 15 wt %, about 0.005 wt % to about 10 wt %, about 0.005 wt % to about 7 wt %, about 0.005 wt % to about 5 wt %, about 0.005 wt % to about 4 wt %, about 0.005 wt % to about 3 wt %, about 0.005 wt % to about 2 wt %, about 0.005 wt % to about 1 wt %, about 0.005 wt % to about 0.5 wt %, about 0.005 wt % to about 0.3 wt %, about 0.01 wt % to about 20 wt %, about 0.01 wt % to about 15 wt %, about 0.01 wt % to about % to about 10 wt %, about 0.01 wt % to about 7 wt %, about 0.01 wt % to about 5 wt %, about 0.01 wt % to about 4 wt %, about 0.01 wt % to about 3 wt %, about 0.01 wt % to about 2 wt %, about 0.01 wt % to about 1 wt %, about 0.01 wt % to about 0.5 wt %, about 0.01 wt % to 0.3 wt %, about 0.05 wt % to about 20 wt %, about 0.05 wt % to about 15 wt %, about 0.05 wt % to about 10 wt %, about 0.05 wt % to about 7 wt %, about 0.05 wt % to about 5 wt %, about 0.05 wt % to about 4 wt %, about 0.05 wt % To about 3 weight %, about 0.05 weight % to about 2 weight %, about 0.05 weight % to about 1 weight %, about 0.05 weight % to about 0.5 weight %, about 0.05 weight % to about 0.3 weight %, about 0.1 weight % to about 20 weight %, about 0.1 weight % to about 15 weight %, about 0.1 weight % to about 10 weight %, about 0.1 weight % to about 7 weight %, about 0.1 weight % to about 5 weight %, about 0.1 weight % to about 4 weight %, about 0.1 weight % to about 3 weight %, about 0.1 weight % to about 2 weight %, about 0.1 weight % to about 1 weight %, about 0.1 weight % to about 0.5 weight %, or about 0.1 weight % to about 0.3 weight %.

[0258] The etching composition as described above may have a pH of about 1.0 to about 8.0, about 1.0 to about 7.0, about 1.0 to about 6.0, about 1.0 to about 5.0, about 1.0 to about 4.0, about 1.0 to about 3.0, about 2.0 to about 8.0, about 2.0 to about 7.0, about 2.0 to about 6.0, about 2.0 to about 5.0, about 2.0 to about 4.0, or about 2.0 to about 3.0. When the pH of the etching composition is within the above range, the interaction between the selective etching inhibitor and the metal atoms in the metal-containing film to be described below may occur more smoothly.

[0259] For example, the etching composition may have a pH of about 1.0 to about 3.0.

[0260] According to an embodiment, the etching composition may be used in an etching process and / or a CMP process of the metal-containing film. For details about the metal-containing film, reference may be made to the description provided herein.

[0261] In one or more embodiments, the etching composition can be used as an agent for removing etching by-products, an agent for removing post-etching by-products, an agent for removing ash by-products, a cleaning composition, a photoresist (PR) remover, an etching composition for a packaging process, a cleaning agent for a packaging process, a wafer adhesive remover, an etchant, a post-etching residue stripper, an ash residue cleaner, a PR residue stripper, a CMP cleaner, a post-CMP cleaner, and the like.

[0262] Metal-containing film etching method and semiconductor device manufacturing method

[0263] The metal-containing film can be effectively etched by using the etching composition as described above.

[0264] Reference Figure 1 According to an embodiment, a method of etching a metal-containing film may include: preparing a substrate having a metal-containing film S100; and performing an etching process of the metal-containing film using an etching composition as described herein to remove at least a portion of the metal-containing film S110.

[0265] For details about the metal-containing film, reference may be made to the description provided herein.

[0266] For example, the metal-containing film may include indium (In), titanium (Ti), aluminum (Al), tungsten (W), lanthanum (La), scandium (Sc), gallium (Ga), zinc (Zn), hafnium (Hf), or any combination thereof.

[0267] In an embodiment, the metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or a combination thereof.

[0268] Since the etching composition includes the copolymer as described above, the etching composition can improve the productivity and efficiency of the etching process while having excellent etching selectivity to the metal-containing film. Therefore, by using the process of etching the metal-containing film using the etching composition as described above, a semiconductor device with excellent performance can be manufactured.

[0269] Figure 2 and 3 is a schematic diagram for explaining an embodiment of a method for etching a metal-containing film.

[0270] Reference Figure 2 , a substrate 100 having a metal-containing film 120 is provided. An intermediate layer 110 may be disposed between the substrate 100 and the metal-containing film 120. Figure 2 Although not shown, circuit elements (e.g., transistor gates and metal lines), impurity regions, and semiconductor layers may be disposed within the substrate 100, on the substrate 100, and / or between the substrate 100 and the intermediate layer 110. According to an embodiment, the metal-containing film 120 may be directly disposed on the substrate 100, and the intermediate layer 110 may be omitted.

[0271] The metal-containing film 120 may include a first region 121 and a second region 122. A second etching rate at which the etching composition etches the second region 122 may be greater than a first etching rate at which the etching composition etches the first region 121.

[0272] Reference Figure 3 The etching composition is used in the etching of the metal-containing film 120 to etch each of at least a portion of the first region 121 and at least a portion of the second region 122, thereby forming a metal-containing film pattern 125. The etching process can be performed by contacting at least a portion of the first region 121 and at least a portion of the second region 122 with the etching composition.

[0273] The etching composition may etch each of at least a portion of the first region 121 and at least a portion of the second region 122. Figure 3 , the metal-containing film pattern 125 formed after etching includes at least a portion of the second region 122. However, if necessary, various modifications are possible, and, for example, the etching process may be performed to completely remove the second region 122 in the metal-containing film pattern 125.

[0274] According to an embodiment, the first region 121 may include at least one of metal oxide (eg, aluminum oxide), silicon oxide, and tungsten.

[0275] According to an embodiment, the second region 122 may include titanium nitride.

[0276] According to an embodiment, the second region 122 may include: i) titanium nitride, ii) titanium nitride further including indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof.

[0277] According to an embodiment, the first region 121 and the second region 122 may each include: i) titanium nitride, ii) titanium nitride further including indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof.

[0278] According to an embodiment, the first region 121 may include tungsten, and the second region 122 may be tungsten-free.

[0279] According to an embodiment, the first region 121 may include tungsten, and the second region 122 may include titanium nitride (TiN).

[0280] According to an embodiment, the first region 121 may be a tungsten film, and the second region 122 may be a titanium nitride (TiN) film.

[0281] According to an embodiment, the etching rate ratio of the second region 122 of the etching composition to the first region 121 may be in the range of about 5 to about 30, about 5 to about 20, about 5 to about 15, or about 10 to about 15. The etching rate ratio of the second region 122 to the first region 121 may be obtained by dividing a second etching rate at which the etching composition etches the second region 122 by a first etching rate at which the etching composition etches the first region 121. When the etching rate ratio of the second region 122 of the etching composition to the first region 121 is within the above range, the efficiency and productivity of the etching process may be improved.

[0282] According to an embodiment, the first region 121 may include tungsten, the second region 122 may include a titanium nitride (TiN) film, and an etching rate ratio of the second region 122 to the first region 121 (hereinafter, referred to as "R(TiN / W)") may be in the range of about 5 to about 30, about 5 to about 20, about 5 to about 15, or about 10 to about 15. R(TiN / W) may be obtained by dividing a rate at which the etching composition etches the second region 122 including the titanium nitride (TiN) film by a rate at which the etching composition etches the first region 121 including the tungsten film.

[0283] Reference Figure 1 , a method of manufacturing a semiconductor device according to an embodiment may include: preparing a substrate having a metal-containing film S100; performing an etching process of the metal-containing film using the etching composition S110; and performing a subsequent manufacturing process to thereby complete the manufacturing of the semiconductor device S120.

[0284] Examples 1 and 2 and Comparative Example 1

[0285] The materials listed in the following Table 1 were mixed in the amounts shown in Table 1 to prepare etching compositions of each of Examples 1 and 2 and Comparative Example 1. In Table 1, the oxidizing agent was hydrogen peroxide, the acid was phosphoric acid, the weight average molecular weight of polymer 1 was 4000 g / mol, and the remainder of each etching composition corresponded to water (deionized water).

[0286] Evaluation Example 1

[0287] The etching composition of Example 1 was added to each of two beakers and heated to 70° C., and then the titanium nitride (TiN) film and the tungsten film that had undergone plasma etching were immersed in each beaker for 5 minutes. Then, the thickness of the TiN film and the tungsten film was measured by using an ellipsometer (M-2000, JA Woolam), a four-point resistance meter, and X-ray fluorescence (XRF) to evaluate the etching rate ( / min) and the etching rate of the tungsten film ( / min). Subsequently, R(TiN / W) of the etching composition of Example 1 was evaluated by dividing the etching rate for the TiN film by the etching rate for the tungsten film, and the results are summarized in Table 1.

[0288] The above test was repeated using the etching compositions of Example 2 and Comparative Example 1, respectively, and the results thereof are summarized in Table 1.

[0289] Table 1

[0290]

[0291]

[0292]

[0293] From Table 1, it can be confirmed that the etching compositions of Examples 1 and 2 can improve the efficiency and productivity of the etching process due to excellent etching selectivity compared with the etching composition of Comparative Example 1.

[0294] According to one or more embodiments, the etching composition can improve the productivity and efficiency of the etching process while having excellent etching selectivity for metal-containing films, so that by using the etching composition, an effective etching process and / or chemical mechanical polishing (CMP) process can be performed on the film to be etched. Therefore, a semiconductor device manufactured by a metal-containing film etching process using the etching composition can have excellent performance.

[0295] It should be understood that the embodiments described herein should be considered in a descriptive sense only and not for limiting purposes. The description of features or aspects within each embodiment should typically be considered to be applicable to other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the accompanying drawings, it will be understood by those of ordinary skill in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the inventive concept as defined by the appended claims.

Claims

1. An etching composition comprising: Oxidants; acid; and Selective etch inhibitors, wherein The oxidant is metal-free, and The selective etching inhibitor comprises a copolymer comprising a first repeating unit and a second repeating unit, The first repeating unit is different from the second repeating unit, and The first repeating unit is a nitrogen-containing repeating unit.

2. The etching composition of claim 1, wherein the oxidizing agent is hydrogen peroxide. 3 . The etching composition of claim 1 , wherein an amount of the oxidizing agent is in a range of 0.1 wt % to 50 wt % relative to 100 wt % of the etching composition.

4. The etching composition of claim 1, wherein the acid comprises at least one of phosphoric acid, hydrochloric acid, and chloric acid.

5. The etching composition of claim 1, wherein the first repeating unit comprises at least one of a repeating unit represented by the following formula 1-1, a repeating unit represented by the following formula 1-2, a repeating unit represented by the following formula 1-3, and a repeating unit represented by the following formula 1-4: Wherein A1 in Formulae 1-1 to 1-3 is *-C(R 16 )(R 17 )-*'、*-N(R 16 )-*', *-C(=O)-*', *-O-*', or *-S-*', a1 in formulas 1-1 to 1-3 is an integer from 0 to 20, wherein, When a1 is 2 or more and less than or equal to 20, at least two A1s are the same as or different from each other, b1 in Formulae 1-1 to 1-4 is an integer from 0 to 10, wherein when b1 is 2 or more and less than or equal to 10, at least two *-C(R 14 )(R 15 )-*' are the same or different from each other, b2 in Formulas 1-3 and 1-4 is an integer from 0 to 10, wherein when b2 is 2 or more and less than or equal to 10, at least two *-C(R 12 )(R 13 )-*' are the same or different from each other, T1 in formulas 1-1 to 1-3 is *-N(Z 11 )(Z 12 )、*-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - , a group represented by the following formula AN, or a group represented by the following formula BN, Rings CY1 to CY4 in Formulas 1-3, 1-4, AN and BN are each independently C2-C 10 Cyclic groups, c1 in Formulas 1-3, 1-4, AN and BN is an integer from 0 to 10, wherein when c1 is 2 or more and less than or equal to 10, at least two R1s are the same as or different from each other, T2 in formula 1-4 and AN is *-N(Z 11 )-*' or *-[N(Z 11 )(Z 12 )] + [Z 14 ] - -*', R1, R 11 To R 17 , and Z 11 To Z 13 Each independently is: Hydrogen, deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q1, *-NH-C(=O)-Q1, *-C(= O)-O-Q1, *-SO2-Q1, *-P(=O)-(Q1)(Q2), *-N(Q1)(Q2), *-[N(Q1)(Q2)(Q3)] + [Q4] - , or *-(O-CH2CH2) n1 -OH; or Each unsubstituted or substituted C1-C 30 Alkyl, C1-C 30 Alkoxy, C2-C 30 Alkenyl, C3-C 30 Carbocyclic group, or C1-C 30 Heterocyclic groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q1, *-NH-C(=O)-Q1, *-C(=O)-O-Q1, *-SO2-Q1, *-P(=O)-(Q1)(Q2), *-N(Q 11 )(Q 12 )、*-[N(Q 11 )(Q 12 )(Q 13 )] + [Q 14 ] - 、*-(O-CH2CH2) n1 -OH, C1-C 30 Alkyl, C1-C 30 Alkoxy, C2-C 30 Alkenyl, C3-C 30 Carbocyclic groups, C1-C 30 Heterocyclic group, or any combination thereof, n1 is an integer from 1 to 20, R1, R 11 To R 17 , and Z 11 To Z 13 At least two of the 10 Cyclic groups, Q1 to Q3 and Q 11 To Q 13 Each independently is: hydrogen, deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH2, *-C(=O)-NH(CH3), *-C(=O)-N(CH3)2, *-NH-C(=O)-NH2, *-NH-C(=O)-NH(CH3), *-NH-C(=O)-N(CH3)2, *-NH2, *-NH(CH3), or *-N(CH3)2; or C1-C 30 Alkyl, C1-C 30 Alkoxy, C2-C 30 Alkenyl, C3-C 30 Carbocyclic group, or C1-C 30 Heterocyclic groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH2, *-C(=O)-NH(CH3), *-C(=O)-N(CH3)2, *-NH-C(=O)-NH2, *-NH-C(=O)-NH(CH3), *-NH-C(=O)-N(CH3)2, *-NH2, *-NH(CH3), *-N(CH3)2, C1-C 30 Alkyl, C1-C 30 Alkoxy, C2-C 30 Alkenyl, C3-C 30 Carbocyclic groups, C1-C 30 Heterocyclic group, or any combination thereof, [Z 14 ] - , [Q4] - and [Q 14 ] - Each is an anion, and * and *' each represent a binding site with an adjacent atom.

6. The etching composition according to claim 5, wherein The first repeating unit includes a repeating unit represented by Formula 1-4, and Ring CY2 in Formula 1-4 is a saturated cyclic group having 4, 5, 6, or 7 carbon atoms.

7. The etching composition according to claim 5, wherein The first repeating unit includes a repeating unit represented by Formula 1-4, and The repeating unit represented by Formula 1-4 is a repeating unit represented by one of Formulas 1-4(1) to 1-4(3), In Formulas 1-4(1) to 1-4(3), b1, b2, R1, R 12 To R 15 , and T2 are each the same as defined in claim 5, c16 is an integer from 0 to 6, c18 is an integer from 0 to 8, and * and *' each represent a binding site with an adjacent atom.

8. The etching composition of claim 1, wherein the second repeating unit comprises at least one of a repeating unit derived from a compound containing sulfur dioxide, a repeating unit derived from a compound containing amide, and a repeating unit derived from a compound containing carboxylic acid.

9. The etching composition of claim 1, wherein the second repeating unit comprises at least one of a repeating unit represented by the following formula 2-1, a repeating unit represented by the following formula 2-2, and a repeating unit represented by the following formula 2-3: in, In formulas 2-1 to 2-3, R 21 and R 22 Each independently is: Hydrogen, deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 21 、*-NH-C(=O)-Q 21 、*-C(=O)-OQ 21 、*-SO2-Q 21 、*-P(=O)-(Q 21 )(Q 22 ), or *-N(Q 21 )(Q 22 );or C1-C 30 Alkyl, C1-C 30 Alkoxy, C2-C 30 Alkenyl, C3-C 30 Carbocyclic group, or C1-C 30 Heterocyclic groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 21 、*-NH-C(=O)-Q 21 、*-C(=O)-OQ 21 、*-SO2-Q 21 、*-P(=O)-(Q 21 )(Q 22 )、*-N(Q 21 )(Q 22 )、C1-C 30 Alkyl, C1-C 30 Alkoxy, C2-C 30 Alkenyl, C3-C 30 Carbocyclic groups, C1-C 30 Heterocyclic group, or any combination thereof, Q 21 and Q 22 Each independently is: hydrogen, deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH2, *-C(=O)-NH(CH3), *-C(=O)-N(CH3)2, *-NH-C(=O)-NH2, *-NH-C(=O)-NH(CH3), *-NH-C(=O)-N(CH3)2, *-NH2, *-NH(CH3), or *-N(CH3)2; or C1-C 30 Alkyl, C1-C 30 Alkoxy, C2-C 30 Alkenyl, C3-C 30 Carbocyclic group, or C1-C 30 Heterocyclic groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH2, *-C(=O)-NH(CH3), *-C(=O)-N(CH3)2, *-NH-C(=O)-NH2, *-NH-C(=O)-NH(CH3), *-NH-C(=O)-N(CH3)2, *-NH2, *-NH(CH3), *-N(CH3)2, C1-C 30 Alkyl, C1-C 30 Alkoxy, C2-C 30 Alkenyl, C3-C 30 Carbocyclic groups, C1-C 30 Heterocyclic group, or any combination thereof, and * and *' each represent a binding site with an adjacent atom.

10. The etching composition according to claim 1, wherein The copolymer further comprises a third repeating unit, and The third repeating unit is different from each of the first repeating unit and the second repeating unit.

11. The etching composition of claim 1, wherein the copolymer comprises at least one of the following polymers 1 to 18: in, In polymers 1 to 18, n, o and p are each independently selected from 1 to 10,000, and * and *' each represent a binding site with an adjacent atom.

12. The etching composition of claim 1, wherein The selective etch inhibitor further comprises an amine-containing compound, and The amine-containing compound is different from the copolymer.

13. The etching composition of claim 12, wherein the amine-containing compound comprises an alkylamine, an alkanolamine, or any combination thereof.

14. The etching composition of claim 1, wherein an amount of the selective etching inhibitor is in a range of 0.001 wt% to 20 wt% relative to 100 wt% of the etching composition.

15. The etching composition of claim 1, wherein the etching composition has a pH of 1.0 to 3.

0.

16. A method of etching a metal-containing film, the method comprising: preparing a substrate having a metal-containing film; and An etching process of the metal-containing film using the etching composition of any one of claims 1 to 15 is performed to remove at least a portion of the metal-containing film.

17. A method for manufacturing a semiconductor device, the method comprising: preparing a substrate having a metal-containing film, performing an etching process of the metal-containing film using the etching composition according to any one of claims 1 to 15 to remove at least a portion of the metal-containing film, and One or more subsequent manufacturing processes are performed to thereby complete the formation of the semiconductor device.

18. The method of claim 16 or 17, wherein the metal-containing film comprises indium (In), titanium (Ti), aluminum (Al), tungsten (W), lanthanum (La), scandium (Sc), gallium (Ga), zinc (Zn), hafnium (Hf), or any combination thereof.

19. The method of claim 16 or 17, wherein The metal-containing film comprises a first region and a second region, The etching process of the metal-containing film using the etching composition etches the first region at a first etching rate and etches the second region at a second etching rate, The second etching rate is higher than the first etching rate, and The etching process includes contacting at least a portion of the first region with the etching composition and contacting at least a portion of the second region with the etching composition.

20. The method of claim 19, wherein The first region includes tungsten, and The second region includes titanium nitride (TiN).

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