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

Abstract

Provided are an etching composition, a method of etching a metal-containing film by using the same, and a method of manufacturing a semiconductor device by using the same. The etching composition may include an oxidizing agent, a buffering agent, and a selective etching inhibitor. The selective etch inhibitor may include a first compound represented by Formula 1 and a second compound different from the first compound. The second compound may include a ring. The ring may be a pyrazole group, an imidazole group, a triazole group, or a tetrazole group, or the ring may be a pyrazole group, an imidazole group, or a triazole group each fused with a phenyl group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, or any combination thereof. The description of Formula 1 is provided in the specification. Formula 1 # imgabs0 #

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is based on and claims the benefit of priority from Korean Patent Application No. 10-2023-0139894 filed in the Korean Intellectual Property Office on October 18, 2023, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

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

[0004] In order to meet the excellent performance and low price required by consumers, it is necessary to improve the integration and reliability of semiconductor devices. As the integration of semiconductor devices increases, damage to the components of semiconductor devices during the process of manufacturing semiconductor devices has a greater impact on the reliability and electrical characteristics of semiconductor memory devices. In particular, in the process of manufacturing semiconductor devices, a variety of etching processes can be performed on a desired and / or alternatively predetermined film (e.g., a metal-containing film). However, in order to perform an effective etching process, there is always a demand for the following etching composition: it is possible to provide excellent etching speed, excellent etching selectivity for adjacent films, no surface residue after etching, excellent storage stability, etc. Summary of the invention

[0005] Provided is an etching composition that improves productivity and efficiency of an etching process while having excellent etching selectivity to a metal-containing film as a target 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 embodiments presented in the disclosure.

[0007] According to an embodiment of the present disclosure, the etching composition may include an oxidant, a buffer and a selective etching inhibitor. The selective etching inhibitor may include a first compound and a second compound represented by Formula 1. The first compound and the second compound may be different from each other. The second compound may include a ring. The ring may be one of the following: a pyrazole group, an imidazole group, a triazole group, or a tetrazole group; or a pyrazole group, an imidazole group, or a triazole group each fused with a phenyl group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, or any combination thereof.

[0008] Formula 1

[0009]

[0010] Among them, in formula 1,

[0011] L 1 C may be unsubstituted or substituted 1 -C 30 Alkylene group: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, or *-SH, or any combination thereof,

[0012] R 1 and R 2 Can be independently one of the following:

[0013] Hydrogen, deuterium, *-OH, or *-SH, or

[0014] C unsubstituted or substituted by 1 -C 30 Alkyl groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, C 1 -C 30 Alkoxy groups, C 1 -C 30 an alkylthio group, or any combination thereof,

[0015] R 11 To R 14 Can be independently one of the following:

[0016] Hydrogen, deuterium, cyano group, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 1 、*-NH-C(=O)-Q 1 、*-C(=O)-OQ 1 、*-N(Q 1 )(Q 2 ), or *-(O-CH 2 CH 2 ) n1 -OH, or

[0017] Each unsubstituted or substituted C 1 -C 30 Alkyl group, C 1 -C 30 Alkoxy groups, C 1 -C 30 Alkylthio group, C 2 -C 30 Alkenyl group, C 3 -C 30 Carbocyclic groups, or C 1 -C 30 Heterocyclic groups: deuterium, cyano groups, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q11 、*-NH-C(=O)-Q 11 、*-C(=O)-OQ 11 、*-N(Q 11 )(Q 12 )、*-(O-CH 2 CH 2 ) n11 -OH, C 1 -C 30 Alkyl group, C 1 -C 30 Alkoxy groups, C 1 -C 30 Alkylthio group, C 2 -C 30 Alkenyl group, C 3 -C 30 Carbocyclic group, C 1 -C 30 Heterocyclic group, or any combination thereof,

[0018] n1 and n11 are each independently an integer from 1 to 20,

[0019] Q 1 , Q 2 , Q 11 and Q 12 Can be independently one of the following:

[0020] 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

[0021] Each unsubstituted or substituted C 1 -C 30 Alkyl group, C 1 -C 30 Alkoxy groups, C 2 -C 30 Alkenyl group, C3 -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 group, C 1 -C 30 Alkoxy groups, C 1 -C 30 Alkylthio group, C 2 -C 30 Alkenyl group, C 3 -C 30 Carbocyclic group, C 1 -C 30 Heterocyclic groups, or any combination thereof, and

[0022] * indicates the binding site with the adjacent atom.

[0023] In some embodiments, the oxidizing agent may be hydrogen peroxide.

[0024] In some embodiments, the amount of the oxidizing agent may be in a range of 0.1 wt % to 50 wt % based on 100 wt % of the etching composition.

[0025] In some embodiments, the buffer can include an ammonium salt.

[0026] In some embodiments, the ammonium salt may include a cation represented by Formula 5-1:

[0027] Formula 5-1

[0028] [N(R 51 )(R 52 )(R 53 )(R 54 )] +

[0029] Among them, in formula 5-1, R 51 To R 54 Can be independently one of the following:

[0030] Hydrogen, or

[0031] C unsubstituted or substituted by 1 -C 30 Alkyl groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, C 1 -C 30 Alkoxy groups, C 1 -C 30 an alkylthio group, or any combination thereof.

[0032] In some embodiments, the ammonium salt may include a phosphate-containing anion, and the phosphate-containing anion may be dihydrogen phosphate ([H 2 PO 4 ] - ), hydrogen phosphate ([HPO 4 ] 2- ), or phosphate ([PO 4 ] 3- ).

[0033] In some embodiments, the amount of the buffer may be in a range of 0.01 wt % to 20 wt % based on 100 wt % of the etching composition.

[0034] In some embodiments, in Formula 1, R 1 and R 2 At least one of them may be unsubstituted or substituted by the following C 1 -C 30 Alkyl groups: *-OH, *-SH, C 1 -C 30 Alkoxy groups, C 1 -C 30 an alkylthio group, or any combination thereof.

[0035] In some embodiments, in Formula 1, R 11 To R 14 At least one of may not be hydrogen.

[0036] In some embodiments, the ring of the second compound may be a pyrazole group, an imidazole group, a triazole group, a tetrazole group, an indazole group, a benzimidazole group, or a benzotriazole group.

[0037] In some embodiments, the second compound may include a compound represented by Formula 2-1 and a

[0038] At least one of the compounds represented by formula 2-2:

[0039]

[0040] Among them, in formulas 2-1 and 2-2,

[0041] X 1 Can be N or C(R 21 ), X 2 Can be N or C(R 22 ), X 3 Can be N or C(R 23 ), X 4 Can be N or C(R 24 ), X 5 Can be N or C(R 25 ), and X 6 Can be N or C(R 26 ), where X in Formula 2-1 1 To X 4 At least one of may be N, and X in Formula 2-2 1 and X 2 At least one of them can be N, R 20 To R 26 Can be independently one of the following:

[0042] Hydrogen, deuterium, cyano group, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 1 、*-NH-C(=O)-Q 1 、*-C(=O)-OQ 1 、*-N(Q 1 )(Q 2 ), or *-(O-CH 2 CH 2 ) n1 -OH, or

[0043] Each unsubstituted or substituted C 1 -C 30 Alkyl group, C 1 -C 30 Alkoxy groups, C 1 -C 30 Alkylthio group, C 2 -C 30 Alkenyl group, C 3 -C 30 Carbocyclic groups, or C 1 -C 30Heterocyclic groups: deuterium, cyano groups, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 11 、*-NH-C(=O)-Q 11 、*-C(=O)-OQ 11 、*-N(Q 11 )(Q 12 )、*-(O-CH 2 CH 2 ) n11 -OH, C 1 -C 30 Alkyl group, C 1 -C 30 Alkoxy groups, C 1 -C 30 Alkylthio group, C 2 -C 30 Alkenyl group, C 3 -C 30 Carbocyclic group, C 1 -C 30 Heterocyclic group, or any combination thereof,

[0044] n1 and n11 may each independently be an integer from 1 to 20, and

[0045] Q 1 , Q 2 , Q 11 and Q 12 Can be independently one of the following:

[0046] 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

[0047] Each unsubstituted or substituted C 1 -C 30 Alkyl group, C 1 -C30 Alkoxy groups, C 2 -C 30 Alkenyl group, 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 group, C 1 -C 30 Alkoxy groups, C 1 -C 30 Alkylthio group, C 2 -C 30 Alkenyl group, C 3 -C 30 Carbocyclic group, C 1 -C 30 A heterocyclic group, or any combination thereof.

[0048] In some embodiments, in Formulas 2-1 and 2-2, R 20 Can be hydrogen or C 1 -C 30 Alkyl group.

[0049] In some embodiments, the amount of the selective etching inhibitor may be in a range of 0.001 wt % to 20 wt % based on 100 wt % of the etching composition.

[0050] In some embodiments, the amount of the first compound may be in the range of 0.001 wt % to 5 wt % based on 100 wt % of the etching composition, and the amount of the second compound may be in the range of 0.001 wt % to 3 wt % based on 100 wt % of the etching composition.

[0051] In some embodiments, the etching composition may have a pH in the range of 6.0 to 9.0.

[0052] According to an embodiment of the present disclosure, a method of etching a metal-containing film may include preparing a substrate including the metal-containing film, and removing at least a portion of the metal-containing film by performing an etching process on the metal-containing film using the etching composition.

[0053] 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), cobalt (Co), copper (Cu), or any combination thereof.

[0054] In some embodiments, the metal-containing film may have a first region and a second region. Performing an etching process on the metal-containing film using the etching composition may include: contacting at least a portion of the first region and at least a portion of the second region with the etching composition, etching the portion of the first region at a first etching rate of the etching composition, and etching the portion of the second region at a second rate of the etching composition. The second etching rate of the etching composition for etching the second region may be greater than the first etching rate of the etching composition for etching the first region.

[0055] In some embodiments, the first region may include Cu or Co, and the second region may include titanium nitride (TiN).

[0056] According to an embodiment of the present disclosure, a method for manufacturing a semiconductor device may include: preparing a substrate including a metal-containing film, removing at least a portion of the metal-containing film by performing an etching process on the metal-containing film using the etching composition, and preparing the semiconductor device by performing a subsequent manufacturing process on a structure having the substrate including the metal-containing film. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] The above and other aspects, features and advantages of some embodiments of the present disclosure will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:

[0058] Figure 1 is a process flow chart of an embodiment of a method for manufacturing a semiconductor device;

[0059] Figure 2 and 3 Each is a diagram briefly illustrating an embodiment of a method of etching a metal-containing film. DETAILED DESCRIPTION

[0060] 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 with reference to the accompanying drawings to illustrate aspects. As used herein, the term "and / or" includes any and all combinations of one or more of the related listed items. When before or after the list of elements, a statement such as "at least one (kind) of ... " modifies the entire list of elements, and does not modify the single element 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. As used herein, the singular forms "one (kind) (indefinite article, a, an)" and "the (said) (the)" are intended to also include plural forms, unless the context clearly states otherwise.

[0061] 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%.

[0062] Target Etching Film

[0063] The target etching film may include a metal-containing film.

[0064] In this regard, the etching composition described below may be used in an etching process and / or a chemical mechanical polishing (CMP) process for a metal-containing film.

[0065] The metal included in the metal-containing film may be an alkali metal (e.g., sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), etc.), an alkaline earth metal (e.g., beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), etc.), a lanthanide metal (e.g., lanthanum (La), europium (Eu), terbium (Tb), ytterbium (Yb), etc.), a transition metal (e.g., scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (H f), 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.

[0066] In an embodiment, the metal-containing film may include In, Ti, Al, Cu, W, Co, La, Sc, Ga, Zn, Hf, or any combination thereof.

[0067] In one or more embodiments, the metal-containing film may include Al, Ti, La, W, Co, Cu, or any combination thereof.

[0068] In one or more embodiments, the metal-containing film may include Ti.

[0069] In one or more embodiments, the metal-containing film may include Ti and Al.

[0070] In one or more embodiments, the metal-containing film may include Cu.

[0071] In one or more embodiments, the metal-containing film may include Co.

[0072] The metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or a combination thereof.

[0073] The metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof, and the metal and the metal included in the metal nitride, metal oxide and metal oxynitride may each include In, Ti, Al, La, Sc, Ga, Zn, Hf, or a combination thereof.

[0074] The metal-containing film may include a metal nitride. The metal included in the metal nitride may include In, Ti, Al, La, Sc, Ga, Zn, Hf, or any combination thereof.

[0075] In one or more embodiments, the metal-containing film may include titanium nitride (TiN). The titanium nitride may further include In, Al, La, Sc, Ga, Hf, Zn, or any combination thereof. In one or more embodiments, the metal-containing film may include titanium nitride, titanium nitride further including Al (e.g., titanium / aluminum nitride (TiAlN)), titanium nitride further including La, etc.

[0076] In one or more embodiments, the metal-containing film may include a metal oxide. The metal included in the metal oxide may include Ti, Al, La, Sc, Ga, Hf, or any combination thereof. In an embodiment, the metal-containing film may include aluminum oxide (e.g., Al 2 O 3 ), indium gallium zinc oxide (IGZO), etc.

[0077] In one or more embodiments, the metal-containing film may include a metal and a metal nitride.

[0078] In one or more embodiments, the metal-containing film may further include metalloids (e.g., boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), etc.), non-metals (e.g., nitrogen (N), phosphorus (P), oxygen (O), sulfur (S), selenium (Se), etc.), or any combination thereof in addition to the above-mentioned metals.

[0079] For example, the metal-containing film may further include silicon oxide.

[0080] The metal-containing film may have a single-layer structure including at least one type of material (or consisting of at least one type of material), or a multilayer structure or pattern structure including materials different from each other. For example, the metal-containing film may have i) a single-layer structure including titanium nitride (or consisting of titanium nitride), ii) a double-layer structure or pattern structure including a first layer including titanium nitride (or consisting of titanium nitride) and a second layer including titanium nitride further including Al (or consisting of titanium nitride further including Al), iii) a double-layer structure or pattern structure including a first layer including titanium nitride (or consisting of titanium nitride) and a second layer including aluminum oxide (or consisting of aluminum oxide), iv) a double-layer structure or pattern structure including a first layer including titanium nitride (or consisting of titanium nitride) and a second layer including Cu or Co (or consisting of Cu or Co), etc.

[0081] In one or more embodiments, the metal-containing film may have a first region and a second region, and a second etching rate for the etching composition for etching the second region may be greater than a first etching rate for the etching composition for etching the first region. In an etching process and / or a CMP process for 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 because the second etching rate is greater than the first etching rate, the second region may be etched faster than the first region.

[0082] The first region and the second region may exist continuously or discontinuously. In addition, a layer (eg, various insulating layers, etc.) may be arranged between the first region and the second region.

[0083] For example, the first region may include metal, metal oxide (eg, aluminum oxide), silicon oxide, or any combination thereof.

[0084] In an embodiment, the first region may include Cu or Co.

[0085] In an embodiment, the second region may include a metal nitride.

[0086] In one or more embodiments, the second region may include: i) titanium nitride, ii) titanium nitride further including In, Al, La, Sc, Ga, Zn, Hf, or any combination thereof, or iii) a combination thereof.

[0087] In one or more embodiments, the first region and the second region each may include: i) titanium nitride, ii) titanium nitride further including In, Al, La, Sc, Ga, Zn, Hf or any combination thereof, or iii) a combination thereof.

[0088] In one or more embodiments, the first region may include Al, and the second region may not include Al.

[0089] In one or more embodiments, the first region may include titanium nitride further including Al (eg, titanium / aluminum nitride (TiAlN)), and the second region may include titanium nitride.

[0090] In one or more embodiments, the first region may include a titanium nitride film further including Al (eg, a titanium / aluminum nitride film (TiAlN film)), and the second region may include a titanium nitride film.

[0091] In one or more embodiments, the first region may be a titanium nitride film further including Al (eg, a titanium / aluminum nitride film (TiAlN film)), and the second region may be a titanium nitride film.

[0092] In one or more embodiments, the first region may include Cu or Co, and the second region may not include Cu or Co.

[0093] In one or more embodiments, the first region may include Cu or Co, and the second region may include titanium nitride (TiN).

[0094] In one or more embodiments, the first region may include a Cu film or a Co film, and the second region may include a titanium nitride film (TiN film).

[0095] In one or more embodiments, the first region may be a Cu film or a Co film, and the second region may be a titanium nitride film (TiN film).

[0096] Etching a film as described herein may refer to removing at least some of the material constituting the film to be etched.

[0097] Etching composition

[0098] The etching composition may include an oxidizing agent, a buffer, and a selective etch inhibitor.

[0099] The etching composition can be used in an etching process and / or a CMP process for a target etching film described herein (eg, the metal-containing film).

[0100] The etching composition may further include water.

[0101] In an embodiment, the etching composition may consist of an oxidizing agent, a buffer, a selective etching inhibitor, and water.

[0102] In one or more embodiments, the etching composition may not include a water-soluble organic solvent, a nitrile-based solvent, a silanol compound, an alkylene glycol-based solvent, and the like.

[0103] Oxidants

[0104] The oxidizing agent may be a substance capable of oxidizing a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof (e.g., a substance capable of oxidizing a metal). For example, anions obtained from the oxidizing agent may be combined with metal-containing cations generated by oxidizing a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof included in a metal-containing film to form a water-soluble complex, which may be used to etch the metal-containing film.

[0105] In an embodiment, the oxidizing agent may not include metals (eg, metal ions, etc.).

[0106] In one or more embodiments, the oxidizing agent may include at least one of hydrogen peroxide, nitric acid, and ammonium sulfate.

[0107] In an embodiment, the oxidizing agent may include hydrogen peroxide.

[0108] For example, in the case where the metal-containing film comprises titanium nitride and the oxidizing agent is hydrogen peroxide, when the etching composition contacts the metal-containing film, HO 2- and Ti-containing cations may combine to form a water-soluble complex, and thus, the metal-containing film may be etched.

[0109] In an embodiment, the amount (weight) of the oxidizing agent may be, for example, in the following ranges based on 100 wt % of the etching composition: 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 25 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 25 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 0.01 wt % to about 25 wt %. .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 25 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 25 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 25 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 %, or about 5.0 wt % to about 25 wt %.

[0110] Buffer

[0111] The buffer can be used to stabilize the etching composition during dilution and / or preparation of the etching composition and to adjust the pH of the etching composition. In addition, the buffer can be used to promote the generation of anions from the oxidant and stabilize the water-soluble complex formed by the combination of the anions and metal-containing cations.

[0112] For example, when the metal-containing film comprises titanium nitride and the oxidant is hydrogen peroxide, the buffer may be used to maintain the HO 2- The high production concentration and the 2- The complex formed in combination with Ti-containing cations is stabilized.

[0113] In embodiments, the buffer may include an ammonium salt.

[0114] In one or more embodiments, the ammonium salt may include a cation represented by Formula 5-1:

[0115] Formula 5-1

[0116] [N(R 51 )(R 52 )(R 53 )(R 54 )] +

[0117] Among them, in formula 5-1, R 51 To R 54 Can be independently:

[0118] Hydrogen; or

[0119] C unsubstituted or substituted by 1 -C 30 Alkyl groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, C 1 -C 30 Alkoxy groups, C 1 -C 30 an alkylthio group, or any combination thereof.

[0120] For example, R 51 To R 54 Can be independently:

[0121] Hydrogen; or

[0122] C unsubstituted or substituted by 1 -C 10 Alkyl groups: deuterium, *-OH, *-SH, C 1 -C 10 Alkoxy groups, C 1 -C 10 an alkylthio group, or any combination thereof.

[0123] In one or more embodiments, the ammonium salt may include an organic anion or an inorganic anion. For example, the organic anion may be a carboxylate-containing anion, and the inorganic anion may be a phosphate-containing anion or a halogen-containing anion.

[0124] In one or more embodiments, the ammonium salt may include a phosphate-containing anion, and the phosphate-containing anion may be dihydrogen phosphate ([H 2 PO 4 ] - ), hydrogen phosphate ([HPO 4 ] 2- ), or phosphate ([PO 4 ] 3- ).

[0125] In one or more embodiments, the buffer may include diammonium phosphate (NH 4 ) 2 (HPO 4 ))、diammonium phosphate ((NH 4 )(H 2 PO 4 )), bis(tetramethylammonium hydrogen phosphate)([N(CH 3 ) 4 ] 2 (HPO 4 ))、Tetramethylammonium dihydrogen phosphate )([N(CH 3 ) 4 ](H 2 PO 4 ))、ammonium phosphate ((NH 4 ) 3 PO 4 ), or any combination thereof.

[0126] The amount by weight of the buffer may be, for example, in the range of about 0.01 wt % to about 20 wt %, about 0.01 wt % to about 15 wt %, about 0.01 wt % to about 10 wt %, about 0.01 wt % to about 5 wt %, about 0.01 wt % to about 3 wt %, about 0.1 wt % to about 20 wt %, about 0.1 wt % to about 15 wt %, about 0.1 wt % to about 10 wt %, about 0.1 wt % to about 5 wt %, about 0.1 wt % to about 3 wt %, about 0.5 wt % to about 20 wt %, about 0.5 wt % to about 15 wt %, about 0.5 wt % to about 10 wt %, about 0.5 wt % to about 5 wt %, or about 0.5 wt % to about 3 wt %, based on 100 wt % of the etching composition.

[0127] Selective Etch Inhibitors

[0128] The selective etching inhibitor can be used to selectively control the etching rate, etc. by forming a protective film (eg, a protective film against etching) on ​​at least a portion of a region of a metal-containing film as a target etching film and / or interacting with at least some of the metal atoms.

[0129] The selective etching inhibitor may include a first compound and a second compound represented by Formula 1. Formula 1 may be the same as described herein.

[0130] Here, the first compound and the second compound may be different from each other. Therefore, the selective etching inhibitor may include two or more different compounds. In this regard, the density and / or adsorption of the protective film formed on at least a portion of the region containing the metal film as the target etching film may be improved, thereby improving the etching selectivity.

[0131] The first compound can be represented by Formula 1:

[0132] Formula 1

[0133]

[0134] Among them, in formula 1,

[0135] L 1 C may be unsubstituted or substituted 1 -C 30 Alkylene group: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, or any combination thereof,

[0136] R 1 and R 2 Can be independently:

[0137] hydrogen, deuterium, *-OH, or *-SH; or

[0138] C unsubstituted or substituted by 1 -C 30 Alkyl groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, C 1 -C 30 Alkoxy groups, C 1 -C 30 an alkylthio group, or any combination thereof,

[0139] R 11 To R 14 Can be independently:

[0140] Hydrogen, deuterium, cyano group, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 1 、*-NH-C(=O)-Q 1 、*-C(=O)-OQ 1 、*-N(Q 1 )(Q 2 ), or *-(O-CH 2 CH2 ) n1 -OH; or

[0141] Each unsubstituted or substituted C 1 -C 30 Alkyl group, C 1 -C 30 Alkoxy groups, C 1 -C 30 Alkylthio group, C 2 -C 30 Alkenyl group, C 3 -C 30 Carbocyclic groups, or C 1 -C 30 Heterocyclic groups: deuterium, cyano groups, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 11 、*-NH-C(=O)-Q 11 、*-C(=O)-OQ 11 、*-N(Q 11 )(Q 12 )、*-(O-CH 2 CH 2 ) n11 -OH, C 1 -C 30 Alkyl group, C 1 -C 30 Alkoxy groups, C 1 -C 30 Alkylthio group, C 2 -C 30 Alkenyl group, C 3 -C 30 Carbocyclic group, C 1 -C 30 Heterocyclic group, or any combination thereof,

[0142] n1 and n11 may each independently be an integer from 1 to 20,

[0143] Q 1 , Q 2 , Q 11 and Q 12 Can be independently:

[0144] 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

[0145] Each unsubstituted or substituted C 1 -C 30 Alkyl group, C 1 -C 30 Alkoxy groups, C 2 -C 30 Alkenyl group, 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 group, C 1 -C 30 Alkoxy groups, C 1 -C 30 Alkylthio group, C 2 -C 30 Alkenyl group, C 3 -C 30 Carbocyclic group, C 1 -C 30 Heterocyclic groups, or any combination thereof, and

[0146] * indicates the binding site with the adjacent atom.

[0147] In an embodiment, L in Formula 11 C may be unsubstituted or substituted 1 -C 10 Alkylene group (or C 1 -C 6 alkylene group): deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, or any combination thereof.

[0148] In one or more embodiments, R in Formula 1 1 and R 2 Can be independently:

[0149] hydrogen, deuterium, *-OH, or *-SH; or

[0150] C unsubstituted or substituted by 1 -C 10 Alkyl groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, C 1 -C 10 Alkoxy groups, C 1 -C 10 an alkylthio group, or any combination thereof.

[0151] In one or more embodiments, R in Formula 1 1 and R 2 Can be the same as each other.

[0152] In one or more embodiments, R in Formula 1 1 and R 2 Can be different from each other.

[0153] In one or more embodiments, R 1 and R 2 At least one of may not be hydrogen.

[0154] In one or more embodiments, R in Formula 1 11 To R 14 Can be independently:

[0155] Hydrogen, deuterium, cyano group, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 1 , or *-N(Q 1 )(Q 2 );or

[0156] C unsubstituted or substituted by 1 -C 10 Alkyl groups: deuterium, cyano groups, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 11 、*-N(Q11 )(Q 12 ), C 1 -C 10 Alkoxy groups, C 1 -C 10 an alkylthio group, or any combination thereof, and

[0157] Q 1 , Q 2 , Q 11 and Q 12 Can be independently:

[0158] 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

[0159] C unsubstituted or substituted by 1 -C 10 Alkyl 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 10 Alkoxy groups, C 1 -C 10an alkylthio group, or any combination thereof.

[0160] For example, Q 1 , Q 2 , Q 11 and Q 12 Can be independently:

[0161] hydrogen, *-OH, *-SH, *-C(=O)-H, or *-C(=O)-OH; or

[0162] C unsubstituted or substituted by 1 -C 10 Alkyl groups: *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, C 1 -C 10 Alkoxy groups, C 1 -C 10 an alkylthio group, or any combination thereof.

[0163] In one or more embodiments, R in Formula 1 1 and R 2 At least one of (e.g., R 1 and R 2 Both) may include *-OH, *-SH, C 1 -C 30 Alkoxy groups, or C 1 -C 30 Alkylthio group.

[0164] In one or more embodiments, R in Formula 1 1 and R 2 At least one of (e.g., R 1 and R 2 Both) may be unsubstituted or substituted by the following C 1 -C 30 Alkyl groups: *-OH, *-SH, C 1 -C 30 Alkoxy groups, C 1 -C 30 In this regard, in the case of *-OH, *-SH, C 1 -C 30 Alkoxy groups, and C 1 -C 30 The bonding between oxygen and / or sulfur included in the alkylthio group and some metal atoms included in the metal-containing film can be improved, so that the density, width, adsorption, etc. of the protective film that can be formed on at least a portion of the region of the metal-containing film can be improved, thereby further improving the etching selectivity of the etching composition.

[0165] In an embodiment, R in Formula 1 11 To R 14 At least one of may not be hydrogen.

[0166] In one or more embodiments, R in Formula 1 11 To R 14 At least one of R may be a hydrophobic substituent. 11 To R 14 At least one of them can be C 1 -C 30 Alkyl group or C 1 -C 10 In this regard, the protective film that may be formed on at least a portion of the region of the metal-containing film may be formed more efficiently.

[0167] The second compound may include a ring, and the ring of the second compound may be:

[0168] a pyrazole group, an imidazole group, a triazole group, or a tetrazole group; or

[0169] a pyrazole group, an imidazole group, or a triazole group each fused to a phenyl group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, or any combination thereof.

[0170] In an embodiment, the ring of the second compound may be a pyrazole group, an imidazole group, a triazole group, a tetrazole group, an indazole group, a benzimidazole group, or a benzotriazole group.

[0171] In one or more embodiments, the second compound may include at least one of a compound represented by Formula 2-1 and a compound represented by Formula 2-2:

[0172]

[0173] Among them, in formula 2-1 and 2-2,

[0174] X 1 Can be N or C(R 21 ), X 2 Can be N or C(R 22 ), X 3 Can be N or C(R 23 ), X 4 Can be N or C(R 24 ), X 5 Can be N or C(R 25 ), and X 6 Can be N or C(R 26 ), where X in Formula 2-1 1 To X 4 At least one of may be N, and X in Formula 2-21 and X 2 At least one of them can be N, R 20 To R 26 Can be independently:

[0175] Hydrogen, deuterium, cyano group, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 1 、*-NH-C(=O)-Q 1 、*-C(=O)-OQ 1 、*-N(Q 1 )(Q 2 ), or *-(O-CH 2 CH 2 ) n1 -OH; or

[0176] Each unsubstituted or substituted C 1 -C 30 Alkyl group, C 1 -C 30 Alkoxy groups, C 1 -C 30 Alkylthio group, C 2 -C 30 Alkenyl group, C 3 -C 30 Carbocyclic groups, or C 1 -C 30 Heterocyclic groups: deuterium, cyano groups, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 11 、*-NH-C(=O)-Q 11 、*-C(=O)-OQ 11 、*-N(Q 11 )(Q 12 )、*-(O-CH 2 CH 2 ) n11 -OH, C 1 -C 30 Alkyl group, C 1 -C 30 Alkoxy groups, C 1 -C 30 Alkylthio group, C 2 -C 30 Alkenyl group, C 3 -C 30 Carbocyclic group, C 1 -C 30 Heterocyclic group, or any combination thereof,

[0177] n1 and n11 may each independently be an integer from 1 to 20,

[0178] Q 1 , Q 2 , Q 11 and Q 12 Can be independently:

[0179] 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

[0180] Each is unsubstituted or substituted by the following C 1 -C 30 Alkyl group, C 1 -C 30 Alkoxy groups, C 2 -C 30 Alkenyl group, 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 group, C 1 -C 30 Alkoxy groups, C 1 -C 30 Alkylthio group, C 2 -C 30 Alkenyl group, C 3 -C 30 Carbocyclic group, C 1 -C 30 Heterocyclic groups, or any combination thereof, and

[0181] * indicates the binding site with the adjacent atom.

[0182] In an embodiment, X in Formula 2-1 1 To X 4 1, 2 or 3 of them can be N.

[0183] In one or more embodiments, in Formula 2-2, X 3 Can be C(R 23 ), X 4 Can be C(R 24 ), X 5 Can be C(R 25 ), and X 6 Can be C(R 26 ).

[0184] In one or more embodiments, in Formula 2-1,

[0185] i)X 1 Can be N, X 2 Can be C(R 22 ), X 3 Can be C(R 23 ), and X 4 Can be C(R 24 ),

[0186] ii)X 1 Can be C(R 21 ), X 2 Can be N, X 3 Can be C(R 23 ), and X 4 Can be C(R 24 ),

[0187] iii)X 1 Can be N, X 2 Can be N, X 3 Can be C(R 23 ), and X 4 Can be C(R 24 ),

[0188] iv)X 1 Can be N, X 2 Can be C(R 22 ), X 3 Can be N, and X 4 Can be C(R 24 ),

[0189] v)X 1 Can be N, X 2 Can be C(R 22 ), X 3 Can be C(R 23 ), and X 4 Can be N,

[0190] vi)X 1 Can be N, X 2 Can be N, X 3 Can be N, and X 4 Can be C(R 24 ),or

[0191] vii)X 1 Can be N, X 2 Can be C(R 22 ), X 3 Can be N, and X 4 Can be N.

[0192] In one or more embodiments, in Formula 2-2,

[0193] 1)X 1 Can be N, X 2 Can be C(R 22 ), X 3 Can be C(R 23 ), X 4 Can be C(R 24 ), X 5 Can be C(R 25 ), and X 6 Can be C(R 26 ),

[0194] 2)X 1 Can be C(R 21 ), X 2 Can be N, X 3 Can be C(R 23 ), X 4 Can be C(R 24 ), X 5 Can be C(R 25 ), and X 6 Can be C(R 26 ),or

[0195] 3)X 1 and X 2 Each can be N, X 3 Can be C(R 23 ), X 4 Can be C(R 24 ), X 5 Can be C(R 25 ), and X 6 Can be C(R 26 ).

[0196] In one or more embodiments, R 20 To R 26 Can be independently:

[0197] Hydrogen, deuterium, cyano group, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 1 , or *-N(Q 1 )(Q 2 );or

[0198] C unsubstituted or substituted by 1 -C 10 Alkyl groups: deuterium, cyano groups, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 11 、*-N(Q 11 )(Q 12 ), C 1 -C 10 Alkoxy groups, C 1 -C 10 An alkylthio group, or any combination thereof. 1 , Q 2 , Q 11 and Q 12 Each may be the same as described in this specification.

[0199] In one or more embodiments, in Formulas 2-1 and 2-2, R 20 To R 26 Can be independently:

[0200] Hydrogen, deuterium, *-F, or *-N(Q 1 )(Q 2 );or

[0201] C unsubstituted or substituted by 1 -C 30 Alkyl groups: deuterium, *-F, *-N(Q 11 )(Q 12 ), or any combination thereof, and

[0202] Q1 , Q 2 , Q 11 and Q 12 can be independently hydrogen, deuterium, or C 1 -C 30 Alkyl group.

[0203] In one or more embodiments, R 20 Can be hydrogen or C 1 -C 30 Alkyl groups (e.g. C 1 -C 10 alkyl group).

[0204] In one or more embodiments, the first compound may be at least one of compounds A1 to A5:

[0205]

[0206] In one or more embodiments, the second compound may be at least one of compounds B1 to B46:

[0207]

[0208]

[0209] The amount (weight) of the selective etching inhibitor may be in the following ranges based on 100 weight % of the etching composition: about 0.001 weight % to about 20 weight %, about 0.001 weight % to about 15 weight %, about 0.001 weight % to about 10 weight %, about 0.001 weight % to about 5 weight %, about 0.001 weight % to about 1 weight %, about 0.001 weight % to about 0.5 weight %, about 0.01 weight % to about 20 weight %, about 0.01 weight % to about 15 weight %, about 0.01 weight % to about 10 weight %, about 0.001 weight % to about 5 weight %, about 0.001 weight % to about 1 weight %, about 0.001 weight % to about 0.5 weight %, about 0.01 weight % to about 20 weight %, about 0.01 weight % to about 15 weight %, about 0.01 weight % to about 10 weight %, about 0.01 weight % to about 5 weight %, about 0.01 weight % to about % to about 1 wt %, about 0.01 wt % to about 0.5 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 5 wt %, about 0.05 wt % to about 1 wt %, about 0.05 wt % to about 0.5 wt %, about 0.1 wt % to about 20 wt %, about 0.1 wt % to about 15 wt %, about 0.1 wt % to about 10 wt %, about 0.1 wt % to about 5 wt %, about 0.1 wt % to about 1 wt %, or about 0.1 wt % to about 0.5 wt %.

[0210] The amount by weight of the first compound may be in the range of about 0.001 wt % to about 5 wt %, about 0.001 wt % to about 3 wt %, about 0.001 wt % to about 1 wt %, about 0.001 wt % to about 0.5 wt %, about 0.05 wt % to about 5 wt %, about 0.05 wt % to about 3 wt %, about 0.05 wt % to about 1 wt %, about 0.05 wt % to about 0.5 wt %, about 0.01 wt % to about 5 wt %, about 0.01 wt % to about 3 wt %, about 0.01 wt % to about 1 wt %, about 0.01 wt % to about 0.5 wt %, about 0.02 wt % to about 5 wt %, about 0.02 wt % to about 3 wt %, about 0.02 wt % to about 1 wt %, or about 0.02 wt % to about 0.5 wt %.

[0211] The amount (weight) of the second compound may be in the range of about 0.001 wt % to about 3 wt %, about 0.001 wt % to about 1 wt %, about 0.001 wt % to about 0.5 wt %, about 0.05 wt % to about 3 wt %, about 0.05 wt % to about 1 wt %, about 0.05 wt % to about 0.5 wt %, about 0.01 wt % to about 3 wt %, about 0.01 wt % to about 1 wt %, about 0.01 wt % to about 0.5 wt %, about 0.02 wt % to about 5 wt %, about 0.02 wt % to about 3 wt %, about 0.02 wt % to about 1 wt %, or about 0.02 wt % to about 0.5 wt %.

[0212] When the amounts of the selective etching inhibitor, the first compound, and the second compound are each within the above range, the etching selectivity of the etching composition may be improved.

[0213] The amount by weight of the first compound may be in the range of about 1 wt % to about 99 wt %, about 10 wt % to about 99 wt %, about 30 wt % to about 99 wt %, about 50 wt % to about 99 wt %, about 70 wt % to about 99 wt %, about 75 wt % to about 99 wt %, about 1 wt % to about 90 wt %, about 10 wt % to about 90 wt %, about 30 wt % to about 90 wt %, about 50 wt % to about 90 wt %, about 70 wt % to about 90 wt %, about 75 wt % to about 90 wt %, about 1 wt % to about 85 wt %, about 10 wt % to about 85 wt %, about 30 wt % to about 85 wt %, about 50 wt % to about 85 wt %, about 70 wt % to about 85 wt %, or about 75 wt % to about 85 wt %.

[0214] In an embodiment, the amount (weight) of the first compound based on 100 wt % of the etching composition may be greater than the amount (weight) of the second compound based on 100 wt % of the etching composition.

[0215] The above-mentioned etching composition may have a pH in the following ranges: about 6.0 to about 9.0, about 6.0 to about 8.5, about 6.0 to about 8.0, about 6.5 to about 9.0, about 6.5 to about 8.5, about 6.5 to about 8.0, about 7.0 to about 9.0, about 7.0 to about 8.5, or about 7.0 to about 8.0. When the etching composition has a pH in the above range, the interaction between the selective etching inhibitor and the metal atoms included in the metal-containing film may be more smoothly achieved.

[0216] In an embodiment, the etching composition can be used in an etching process and / or a CMP process for a metal-containing film. The metal-containing film can be the same as described herein.

[0217] In an embodiment, the etching composition can be used as an etching by-product remover, a post-etching process by-product remover, an ashing process by-product remover, a cleaning composition, a photoresist (PR) remover, an etching composition for a packaging process, a cleaning agent for a packaging process, a remover of adhesive substances for wafers, 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.

[0218] Metal-containing film etching method and semiconductor device manufacturing method

[0219] By using the above-mentioned etching composition, a metal-containing film can be efficiently etched.

[0220] refer to Figure 1 , an embodiment of the etching method of the metal-containing film may include: preparing a substrate provided with the metal-containing film S100; and performing an etching process using the etching composition on the metal-containing film S110 to remove at least a portion of the metal-containing film.

[0221] The metal-containing film may be the same as described herein.

[0222] In embodiments, the metal-containing film may include In, Ti, Al, W, La, Sc, Ga, Zn, Hf, Co, Cu, or any combination thereof.

[0223] In one or more embodiments, the metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or a combination thereof.

[0224] By including the selective etching inhibitor, the etching composition can have excellent etching selectivity for the metal-containing film, and can improve the productivity and efficiency of the etching process. Therefore, by using the etching process for the metal-containing film using the above-mentioned etching composition, a semiconductor device with excellent performance can be prepared.

[0225] Figure 2 and 3 Each is a diagram briefly illustrating an embodiment of a method of etching a metal-containing film.

[0226] refer to Figure 2 , a substrate 100 provided with a metal-containing film 120 may be 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, metal lines, etc.), impurity regions, semiconductor layers, etc. may be disposed within substrate 100, on substrate 100, and / or between substrate 100 and intermediate layer 110. In an embodiment, metal-containing film 120 may be directly disposed on substrate 100, and intermediate layer 110 may be omitted.

[0227] The metal-containing film 120 may include a first region 121 and a second region 122. A second etching rate of the etching composition for etching the second region 122 may be greater than a first etching rate of the etching composition for etching the first region 121.

[0228] refer to Figure 3 When the etching composition is used to etch the metal-containing film 120, i) only at least a portion of the second region 122 may be etched, or ii) at least a portion of the second region 122 and at least a portion of the first region 121 may be etched, thereby forming a metal-containing film pattern 125. The etching process may 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.

[0229] The etching composition may be used to etch i) only at least a portion of the second region 122, or ii) at least a portion of the second region 122 and at least a portion of the first region 121. Figure 3 The metal-containing film pattern 125 formed after etching includes at least a portion of the second region 122, but if necessary, an etching process may be performed to completely remove the second region 122 from the metal-containing film pattern 125. Likewise, various modifications may be performed.

[0230] In one or more embodiments, the first region 121 may include metal oxide (eg, aluminum oxide), silicon oxide, W, Co, Cu, or any combination thereof.

[0231] In one or more embodiments, the second region 122 may include titanium nitride.

[0232] In one or more embodiments, the second region 122 may include i) titanium nitride, ii) titanium nitride further including In, Al, La, Sc, Ga, Zn, Hf, or any combination thereof, or iii) a combination thereof.

[0233] In one or more embodiments, the first region 121 and the second region 122 may each include i) titanium nitride, ii) titanium nitride further including In, Al, La, Sc, Ga, Zn, Hf, or any combination thereof, or iii) a combination thereof.

[0234] In one or more embodiments, the first region 121 may include Cu or Co, and the second region 122 may not include Cu or Co.

[0235] In one or more embodiments, the first region 121 may include Cu or Co, and the second region 122 may include titanium nitride (TiN).

[0236] In one or more embodiments, the first region 121 may be a Cu film or a Co film, and the second region 122 may be a titanium nitride film (TiN film).

[0237] In one or more embodiments, 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 120 to about 500, about 150 to about 500, about 170 to about 500, about 176 to about 500, about 120 to about 400, about 150 to about 400, about 170 to about 400, about 176 to about 400, about 120 to about 300, about 150 to about 300, about 170 to about 300, about 176 to about 300, or about 176 to about 211. The etching rate ratio of the second region 122 of the etching composition to the first region 121 may be obtained by dividing the second etching rate of the etching composition for etching the second region 122 by the first etching rate of the etching composition for etching 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.

[0238] In one or more embodiments, the first region 121 may include Cu, the second region 122 may include a titanium nitride film (TiN thin film), and an etching rate ratio of the second region 122 to the first region 121 of the etching composition (hereinafter referred to as "R(TiN / Cu)") may be in the following range: about 120 to about 500, about 150 to about 500, about 170 to about 500, about 176 to about 500, about 120 to about 400, about 150 to about 400, about 170 to about 400, about 176 to about 400, about 120 to about 300, about 150 to about 300, about 170 to about 300, about 176 to about 300, or about 176 to about 211. R(TiN / Cu) can be obtained by dividing the etching rate of the etching composition for etching the second region 122 including the titanium nitride film ((TiN film)) by the etching rate of the etching composition for etching the first region 121 including the Cu film.

[0239] In one or more embodiments, the first region 121 may include Cu or Co, and the etching composition may be used in a wet etching process requiring suppression of etching of the first region 121 .

[0240] In one or more embodiments, the etching composition may be used to etch a metal-containing film and simultaneously remove dry etching residues.

[0241] refer to Figure 1 According to an embodiment, a method for manufacturing a semiconductor device may include: preparing a substrate provided with a metal-containing film S100; performing an etching process using an etching composition on the metal-containing film to remove at least a portion of the metal-containing film S110; and manufacturing a semiconductor device by performing a subsequent process S120 on a structure having the substrate having the metal-containing film.

[0242] Examples 1 and 2 and Comparative Examples 1 to 5

[0243] An etching composition was prepared for each of Examples 1 and 2 and Comparative Examples 1 to 5 by mixing the materials shown in Table 1 with the amounts shown in Table 1. In Table 1, the oxidizing agent is hydrogen peroxide, the buffer is (NH 4 ) 2 HPO 4 , and the remainder of each etching composition is water (deionized water).

[0244] Evaluation Example 1

[0245] The etching composition of Example 1 was placed in two beakers and heated to 70° C. Then, the plasma-etched titanium nitride film (TiN film) and copper film (Cu film) were immersed in each beaker for 5 minutes, and the thickness of the TiN film and the Cu film were measured using an ellipsometer (M-2000, JA Woolam), a 4-point probe, and XRF (X-ray fluorescence spectrometry). Then, the etching rate of the etching composition of Example 1 for etching the TiN film was evaluated separately. and the etching rate of the etching composition of Example 1 for etching a Cu film Subsequently, R(TiN / Cu) of the etching composition of Example 1 was obtained by dividing the etching rate of the etching composition for etching a TiN film by the etching rate of the etching composition for etching a Cu film and evaluated, and the results are summarized in Table 1.

[0246] The above test was repeated by using the etching compositions of Example 2 and Comparative Examples 1 to 5, and the results are summarized in Table 1 together with the pH of each etching composition.

[0247] Table 1

[0248]

[0249]

[0250] Referring to Table 1, the etching compositions of Examples 1 and 2 have excellent etching selectivity compared to the etching compositions of Comparative Examples 1 to 5, thereby improving the efficiency and productivity of the etching process.

[0251] According to one or more embodiments, the etching composition may have excellent etching selectivity for a metal-containing film as a target etching film and may be able to improve the productivity and efficiency of the etching process, and thus the use of the etching composition may result in an effective (efficient) etching process and / or chemical mechanical polishing process for the target etching film. Therefore, a semiconductor device prepared by using an etching process for a metal-containing film using the etching composition may have excellent performance.

[0252] 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 in 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 defined by the appended claims.

Claims

1. An etching composition comprising: Oxidants; Buffers; and Selective etch inhibitors, wherein The selective etching inhibitor includes a first compound and a second compound represented by Formula 1, the first compound and the second compound are different from each other, The second compound includes a ring, and The ring of the second compound is one of the following: a pyrazole group, an imidazole group, a triazole group, or a tetrazole group; or a pyrazole group, an imidazole group, or a triazole group, each fused to a phenyl group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, or any combination thereof, Formula 1 Among them, in formula 1, L1 is unsubstituted or substituted with C1-C 30 Alkylene group: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, or any combination thereof, R1 and R2 are each independently one of the following: Hydrogen, deuterium, *-OH, or *-SH, or C1-C 30 Alkyl groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, C1-C 30 Alkoxy groups, C1-C 30 an alkylthio group, or any combination thereof, R 11 To R 14 Each independently is one of the following: Hydrogen, deuterium, cyano group, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q1, *-NH-C(=O)-Q1, *-C(=O)-O-Q1, *-N(Q1)(Q2), or *-(O-CH2CH2) n1 -OH, or Each of C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C1-C 30 Alkylthio group, C2-C 30 Alkenyl groups, C3-C 30 Carbocyclic group, or C1-C 30 Heterocyclic groups: deuterium, cyano groups, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 11 、*-NH-C(=O)-Q 11 、*-C(=O)-OQ 11 、*-N(Q 11 )(Q 12 )、*-(O-CH2CH2) n11 -OH, C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C1-C 30 Alkylthio group, C2-C 30 Alkenyl groups, C3-C 30 Carbocyclic groups, C1-C 30 Heterocyclic group, or any combination thereof, n1 and n11 are each independently an integer from 1 to 20, Q1, Q2, Q 11 and Q 12 Each independently is one of the following: 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 Each of C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C2-C 30 Alkenyl groups, 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 groups, C1-C 30 Alkoxy groups, C1-C 30 Alkylthio group, C2-C 30 Alkenyl groups, C3-C 30 Carbocyclic groups, C1-C 30 Heterocyclic groups, or any combination thereof, and * indicates the binding site with the adjacent atom.

2. The etching composition according to claim 1, wherein the oxidizing agent is hydrogen peroxide. 3 . The etching composition according to claim 1 , wherein the amount of the oxidizing agent is in the range of 0.1 wt % to 50 wt % based on 100 wt % of the etching composition. The etching composition of claim 1 , wherein the buffer comprises an ammonium salt.

5. The etching composition according to claim 4, wherein the ammonium salt comprises a cation represented by Formula 5-1: Formula 5-1 [N(R 51 )(R 52 )(R 53 )(R 54 )] + in, In formula 5-1, R 51 To R 54 Each independently is one of the following: Hydrogen, or C1-C 30 Alkyl groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, C1-C 30 Alkoxy groups, C1-C 30 an alkylthio group, or any combination thereof.

6. The etching composition according to claim 4, wherein The ammonium salt includes a phosphate-containing anion, and The phosphate-containing anion is dihydrogen phosphate ([H2PO4] - ), hydrogen phosphate ([HPO4] 2- ), or phosphate ([PO4] 3- ). 7 . The etching composition according to claim 1 , wherein an amount of the buffer is in a range of 0.01 wt % to 20 wt % based on 100 wt % of the etching composition.

8. The etching composition according to claim 1, wherein at least one of R1 and R2 is unsubstituted or substituted with C1-C 30 Alkyl groups: *-OH, *-SH, C1-C 30 Alkoxy groups, C1-C 30 an alkylthio group, or any combination thereof.

9. The etching composition according to claim 1, wherein R 11 To R 14 At least one of is not hydrogen. 10 . The etching composition according to claim 1 , wherein the ring of the second compound is a pyrazole group, an imidazole group, a triazole group, a tetrazole group, an indazole group, a benzimidazole group, or a benzotriazole group.

11. The etching composition according to claim 1, wherein the second compound comprises at least one of a compound represented by Formula 2-1 and a compound represented by Formula 2-2: in, In formulas 2-1 and 2-2, X1 is N or C (R 21 ), X2 is N or C (R 22 ), X3 is N or C (R 23 ), X4 is N or C (R 24 ), X5 is N or C (R 25 ), and X6 is N or C (R 26 ), wherein at least one of X1 to X4 in Formula 2-1 is N, and at least one of X1 and X2 in Formula 2-2 is N, R 20 To R 26 Each independently is one of the following: Hydrogen, deuterium, cyano group, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q1, *-NH-C(=O)-Q1, *-C(=O)-O-Q1, *-N(Q1)(Q2), or *-(O-CH2CH2) n1 -OH, or Each of C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C1-C 30 Alkylthio group, C2-C 30 Alkenyl groups, C3-C 30 Carbocyclic group, or C1-C 30 Heterocyclic groups: deuterium, cyano groups, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 11 、*-NH-C(=O)-Q 11 、*-C(=O)-OQ 11 、*-N(Q 11 )(Q 12 )、*-(O-CH2CH2) n11 -OH, C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C1-C 30 Alkylthio group, C2-C 30 Alkenyl groups, C3-C 30 Carbocyclic groups, C1-C 30 Heterocyclic group, or any combination thereof, n1 and n11 are each independently an integer from 1 to 20, Q1, Q2, Q 11 and Q 12 Each independently is one of the following: 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 Each of C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C2-C 30 Alkenyl groups, 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 groups, C1-C 30 Alkoxy groups, C1-C 30 Alkylthio group, C2-C 30 Alkenyl groups, C3-C 30 Carbocyclic groups, C1-C 30 Heterocyclic groups, or any combination thereof, and * indicates the binding site with the adjacent atom.

12. The etching composition according to claim 11, wherein R 20 is hydrogen or C1-C 30 Alkyl group. 13 . The etching composition according to claim 1 , wherein an amount of the selective etching inhibitor is in a range of 0.001 wt % to 20 wt % based on 100 wt % of the etching composition.

14. The etching composition according to claim 1, wherein The amount of the first compound is in the range of 0.001 wt % to 5 wt % based on 100 wt % of the etching composition, and The amount of the second compound is in the range of 0.001 wt % to 3 wt % based on 100 wt % of the etching composition.

15. The etching composition of claim 1, wherein the etching composition has a pH in the range of 6.0 to 9.

0.

16. A method of etching a metal-containing film, the method comprising: preparing a substrate including a metal-containing film; and At least a portion of the metal-containing film is removed by performing an etching process on the metal-containing film using the etching composition according to any one of claims 1 to 15.

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

18. The method according to claim 16, wherein The metal-containing film has a first region and a second region, The etching process of the metal-containing film using the etching composition comprises: contacting at least a portion of the first region and at least a portion of the second region with the etching composition, etching the portion of the first region at a first etching rate of the etching composition, and etching the portion of the second region at a second etching rate of the etching composition, and A second etch rate of the etching composition for etching the second region is greater than a first etch rate of the etching composition for etching the first region.

19. The method according to claim 18, wherein The first region comprises copper or cobalt, and The second region includes titanium nitride (TiN).

20. A method for manufacturing a semiconductor device, the method comprising: preparing a substrate including a metal-containing film; removing at least a portion of the metal-containing film by performing an etching process on the metal-containing film using the etching composition according to any one of claims 1 to 15; and The structure having the substrate including the metal-containing film is subjected to a subsequent manufacturing process.

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