Composition, processing method for metal-containing film using the same, and manufacturing method for semiconductor element using the same

Abstract

To provide a composition, a processing method for a metal-containing film using the same, and a manufacturing method for a semiconductor element using the same.SOLUTION: A composition includes an oxide, an acid, and a selective etching inhibitor. The selective etching inhibitor includes a polymer having a nitrogen-containing repeating unit, and an ammonium compound. A processing method for a metal-containing film using this composition, and a manufacturing method for a semiconductor element using this composition are also provided.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a composition, a method for treating a metal-containing film using the same, and a method for manufacturing a semiconductor device using the same. [Background technology]

[0002] To meet consumer demands for superior performance and low prices, semiconductor devices are required to have increased integration density and improved reliability. As integration density increases, damage to components of semiconductor devices during the manufacturing process of semiconductor devices has a greater impact on the reliability and electrical characteristics of semiconductor memory devices. In particular, various processing steps, such as etching, cleaning, and polishing, are performed on a given film (e.g., a metal-containing film) during the manufacturing process of semiconductor devices. In order to effectively perform the metal-containing film processing steps, there is a continuing need for compositions having appropriate etching rates. Summary of the Invention [Problem to be solved by the invention]

[0003] The present invention provides a composition capable of effectively controlling the etching rate of various metal-containing films, a method for treating a metal-containing film using the composition, and a method for manufacturing a semiconductor device using the composition. [Means for solving the problem]

[0004] In one aspect, a composition is provided that includes an oxidizing agent, an acid, and a selective etch inhibitor, the selective etch inhibitor including a polymer having a nitrogen-containing repeating unit and an ammonium compound (e.g., an ammonium salt).

[0005] The oxidizing agent may include hydrogen peroxide.

[0006] The acid may include phosphoric acid.

[0007] The nitrogen-containing repeating unit may include 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, a repeating unit represented by the following formula 1-4, or any combination thereof: [ka]

[0008] In chemical formulas 1-1 to 1-3, A1 is *-C(R 16 )(R 17 )-*', *-N(R 16 )-*', *-C(=O)-*', *-O-*', or *-S-*', In Chemical Formulae 1-1 to 1-3, a1 represents an integer of 0 to 20, and when a1 is 2 or more, the two or more A1 may be the same or different from each other. In Chemical Formulas 1-1 to 1-4, b1 is an integer of 0 to 10, and when b1 is 2 or more, two or more *-C(R 14 )(R 15 )-*' may be the same or different from each other, In chemical formulas 1-1 to 1-3, T1 is *-N(Z 11 )(Z 12 ), *-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - , a group represented by the following chemical formula AN, or a group represented by the following chemical formula BN, [ka] In the chemical formulae 1-3, 1-4, AN, and BN, rings CY1 to CY4 are each independently a cyclic group having 2 to 10 carbon atoms, In the above formulas 1-3, 1-4, AN and BN, c1 is selected from integers of 0 to 10, and when c1 is 2 or more, two or more R1 may be the same or different from each other; In the above chemical formulas 1-4 and AN, T2 is *-N(Z 11 )-*' or *-[N(Z 11 )(Z 12 )] + [Z 14 ] - -*', The R1 and R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , Z 11 , Z 12 and Z 13 are independent of each other, 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 Deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 11 , *-NH-C(=O)-Q 11 , *-C(=O)-OQ 11 , *-SO2-Q 11 , *-P(=O)-(Q 11 )(Q 12 ), *-N(Q 11 )(Q 12 ), *-[N(Q 11 )(Q 12 )(Q 13 )] + [Q 14 ] - , *-(O-CH2CH2) n2 -OH, C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C2-C 30 Alkenyl groups, C3-C 30 carbocyclic group, C1-C 30heterocyclic groups, or any combination thereof, substituted or unsubstituted, C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C2-C 30 Alkenyl groups, C3-C 30 Carbocyclic group, or C1-C 30 a heterocyclic group; n1 and n2 are each independently an integer of 1 to 20, The R1 and R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , Z 11 , Z 12 and Z 13 two or more of which can optionally be bonded to each other to form a cyclic group having 2 to 10 carbon atoms; Q1 to Q3 and Q 11 ~Q 13 are independent of each other, 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 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, C2-C 30 Alkenyl groups, C3-C 30 carbocyclic group, C1-C 30heterocyclic groups, or any combination thereof, substituted or unsubstituted, C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C2-C 30 Alkenyl groups, C3-C 30 Carbocyclic group, or C1-C 30 a heterocyclic group; [Z 14 ] - , [Q4] - and [Q 14 ] - Each is an anion, Each * and *' is a bonding site with an adjacent atom.

[0009] The ammonium compound is [N(X1)(X2)(X3)(X4)] + wherein X1 to X4 are each independently hydrogen or C1-C 20 It is an alkyl group.

[0010] the ammonium compound comprises an anion; The anion is F - , Cl - , Br - , I - , [OH] - , [(R 10 )CO2] - , [CO3] 2- , [NO3] - , [SO4] 2- , [(R 10 )SO4] - , [(R 10 )SO3] - , [C6H7O7] - , [C6H6O7] 2- , [C6H5O7] 3- , [PO3] 3- , [SO3] 2- , [C2O4] 2- , [C4H4O6] 2- , [C5H8NO4] - , [C7H5O3] - , [BF4] - or any combination thereof, R 10 teeth, hydrogen, deuterium, *-OH, *-SH, or *-NH2; or Deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-NH2, *-C(=O)-OH, C1-C 20 Alkyl groups, C1-C 20 C1-C substituted or unsubstituted alkoxy groups, or any combination thereof 20 Alkyl groups, C2-C 20 Alkenyl groups, C1-C 20 Alkoxy groups, C6-C 20 Aryl group, or C2-C 20 a heteroaryl group;

[0011] According to another aspect, providing a substrate having a metal-containing film provided thereon; contacting the metal-containing film with the composition.

[0012] The metal contained in the metal-containing film may include titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

[0013] The metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.

[0014] Contacting the metal-containing film with the composition may etch, clean, or polish one or more portions of the metal-containing film.

[0015] According to yet another aspect, providing a substrate having a metal-containing film provided thereon; contacting the metal-containing film with the composition; and performing subsequent manufacturing process(es) to fabricate the semiconductor device. [Effects of the Invention]

[0016] The composition can easily control the etching rate of various metal-containing films, and therefore can be effectively used in various treatment processes for the metal-containing film, such as etching, cleaning, and polishing processes. By treating a metal-containing film with the composition, high-quality semiconductor devices can be produced. [Brief explanation of the drawings]

[0017] [Figure 1] 1 is a process flowchart of one embodiment of a method for manufacturing a semiconductor device. DETAILED DESCRIPTION OF THE INVENTION

[0018] metal-containing film The metal contained 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 lanthanum group 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), etc.). , 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.), post-transition metals (e.g., aluminum (Al), gallium (Ga), indium (In), thallium (Tl), tin (Sn), bismuth (Bi), etc.), or any combination thereof.

[0019] According to one embodiment, the metal contained in the metal-containing film comprises titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

[0020] For example, the metal-containing film may include aluminum, titanium, lanthanum, tungsten, or any combination thereof.

[0021] As yet another example, the metal-containing film includes titanium and tungsten.

[0022] The metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.

[0023] According to one embodiment, the metal-containing film includes a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof, and the metal included in each of the metal nitride, metal oxide, and metal oxynitride includes titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

[0024] According to another embodiment, the metal-containing film comprises a metal nitride, wherein the metal contained in the metal nitride comprises indium, titanium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, tungsten, or any combination thereof.

[0025] For example, the metal-containing film may include titanium nitride. The titanium nitride may further include indium, aluminum, lanthanum, scandium, gallium, hafnium, zinc, tungsten, or any combination thereof. As yet another example, the metal-containing film may include titanium nitride (TiN), titanium nitride further including aluminum (e.g., titanium / aluminum nitride or TiAlN), titanium nitride further including lanthanum, etc.

[0026] In yet another example, the metal-containing film includes a metal oxide. The metal included in the metal oxide includes titanium, aluminum, lanthanum, scandium, gallium, hafnium, or any combination thereof. For example, the metal-containing film includes aluminum oxide (e.g., Al2O3), IGZO (indium gallium zinc oxide), etc.

[0027] As yet another example, the metal-containing film includes the metal nitride and the metal oxide.

[0028] As yet another example, the metal-containing film may further include, in addition to a metal, a semimetal (e.g., boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), etc.), a nonmetal (e.g., nitrogen (N), phosphorus (P), oxygen (O), sulfur (S), selenium (Se), etc.), and any combination thereof.

[0029] For example, the metal-containing film may further include silicon oxide.

[0030] The metal-containing film may have a single layer structure containing one or more materials, or a multilayer structure or three-dimensional pattern structure containing different materials. For example, the metal-containing film may have: i) a single layer structure containing (or consisting of) titanium nitride; ii) a double layer structure or three-dimensional pattern structure containing a first layer containing (or consisting of) titanium nitride and a second layer containing (or consisting of) titanium nitride further containing aluminum; iii) a double layer structure or three-dimensional pattern structure containing a first layer containing (or consisting of) titanium nitride and a second layer containing (or consisting of) aluminum oxide; or iv) a double layer structure or three-dimensional pattern structure containing a first layer containing (or consisting of) titanium nitride and a second layer containing (or consisting of) tungsten.

[0031] composition The composition includes an oxidizer, an acid, and a selective etch inhibitor.

[0032] The compositions can be used in a variety of processing steps, such as etching, cleaning, polishing, etc., on metal-containing films described herein.

[0033] The composition may further comprise water.

[0034] According to one embodiment, the composition may consist of an oxidizer, an acid, a selective etch inhibitor, and water.

[0035] oxidizing agent The oxidizing agent serves to etch at least a portion of the metal-containing film and may include, for example, at least one of hydrogen peroxide, nitric acid, and ammonium sulfate.

[0036] According to one embodiment, the oxidizing agent comprises hydrogen peroxide.

[0037] According to another embodiment, the oxidizing agent is hydrogen peroxide.

[0038] The content (weight) of the oxidizing agent is, for example, 0.001 wt% to 50 wt%, 0.01 wt% to 50 wt%, 0.1 wt% to 50 wt%, 0.5 wt% to 50 wt%, 1 wt% to 50 wt%, 0.001 wt% to 30 wt%, 0.01 wt% to 30 wt%, 0.1 wt% to 30 wt%, 0.5 wt% to 30 wt%, 1 wt% to 30 wt%, t%, 0.001wt% to 20wt%, 0.01wt% to 20wt%, 0.1wt% to 20wt%, 0.5wt% to 20wt%, 1wt% to 20wt%, 0.001wt% to 10wt%, 0.01wt% to 10wt%, 0.1wt% to 10wt%, 0.5wt% to 10wt%, 1wt% to 10wt%, 2wt% to 8wt%, or 3wt% to 6wt%.

[0039] acid The acid may act in conjunction with the oxidizing agent to etch at least a portion of the metal-containing layer.

[0040] The acid may comprise an inorganic acid, an organic acid, or any combination thereof.

[0041] According to one embodiment, the acid comprises a phosphorus-based inorganic acid, a chlorine-based inorganic acid, a fluorine-based inorganic acid, or any combination thereof. For example, the phosphorus-based inorganic acid is a phosphate-based inorganic acid.

[0042] According to another embodiment, the acid does not include at least one of nitric acid and sulfuric acid.

[0043] According to yet another embodiment, the acid comprises at least one of a phosphoric acid and a chlorine-based inorganic acid.

[0044] According to yet another embodiment, the acid comprises at least one of phosphoric acid, hydrochloric acid, and chloric acid.

[0045] According to yet another embodiment, the acid comprises phosphoric acid.

[0046] The content (weight) of the acid is, for example, 0.01 wt% to 90 wt%, 0.1 wt% to 90 wt%, 1 wt% to 90 wt%, 10 wt% to 90 wt%, 20 wt% to 90 wt%, 30 wt% to 90 wt%, 40 wt% to 90 wt%, 50 wt% to 90 wt%, 60 wt% to 90 wt%, 0.01 wt% to 80 wt%, 0.1 wt% to 80 wt%, 1 wt% to 80 wt%, 10 wt% to 80 wt%, 20 wt% to 80 wt%, 30 wt% to 80 wt%, 40 wt% to 80 wt%, 50 wt% to 80 wt%, or 60 wt% to 80 wt%, per 100 wt% of the composition.

[0047] Selective Etching Inhibitors The selective etching inhibitor may interact with various metal atoms in the metal-containing film, which is the film to be treated, and thereby adjust the etching rate.

[0048] The selective etch inhibitor comprises a polymer having a nitrogen-containing repeating unit and an ammonium compound.

[0049] Polymers with nitrogen-containing repeating units included in selective etching inhibitors The polymer having nitrogen-containing repeating units contained in the selective etching inhibitor is also a water-soluble polymer.

[0050] The polymer having the nitrogen-containing repeating unit can protect the surface of the metal-containing film through electrostatic attraction. Furthermore, because the polymer having the nitrogen-containing repeating unit has a bulky three-dimensional structure, it can effectively protect at least a portion of the surface of the metal-containing film. This allows the composition to be used to treat the metal-containing film described herein for various purposes (e.g., etching, cleaning, polishing, etc.).

[0051] The nitrogen-containing repeating unit may include 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, a repeating unit represented by the following formula 1-4, or any combination thereof: [ka]

[0052] In chemical formulas 1-1 to 1-3, A1 is *-C(R 16 )(R 17 )-*', *-N(R 16 )-*', *-C(=O)-*', *-O-*', or *-S-*'. In Chemical Formulae 1-1 to 1-3, a1 is an integer of 0 to 20, and when a1 is 2 or more, the two or more A1 may be the same or different. When a1 is 0, *-(A1) a1 -*' is a single bond.

[0053] According to one embodiment, said a1 is 0.

[0054] According to another embodiment, said a1 is not zero.

[0055] According to yet another embodiment, a1 is an integer of 0-10.

[0056] According to yet another embodiment, a1 is an integer of 1-5.

[0057] In Chemical Formulas 1-1 to 1-4, b1 is an integer of 0 to 10, and when b1 is 2 or more, two or more *-C(R 14 )(R 15 )-*' may be the same as or different from each other. When b1 is 0, *-C(R 14 )(R 15 )-*' is a single bond.

[0058] According to one embodiment, b1 is an integer of 0-5.

[0059] In chemical formulas 1-1 to 1-3, T1 is *-N(Z 11 )(Z 12 ), *-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - , a group represented by the following chemical formula AN, or a group represented by the following chemical formula BN: [ka]

[0060] In the above chemical formulae 1-3, 1-4, AN and BN, rings CY1 to CY4 are each independently a cyclic group having 2 to 10 carbon atoms.

[0061] In the above chemical formulas 1-4 and AN, T2 is *-N(Z 11 )-*' or *-[N(Z 11 )(Z 12 )] + [Z 14 ] - -*'. Z 11 , Z 12 and Z 14 For the respective descriptions, please refer to the descriptions in this specification.

[0062] According to one embodiment, in Chemical Formulas 1-1 to 1-3, T1 is *-N(Z 11 )(Z 12 ) or *-[N(Z 11 )(Z12 )(Z 13 )] + [Z 14 ] - and Z 11 ~Z 13 Each is hydrogen.

[0063] According to another embodiment, in the chemical formulas 1-1 to 1-3, T1 is *-N(Z 11 )(Z 12 ) or *-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - and Z 11 is hydrogen, and Z 12 is not hydrogen.

[0064] According to still another embodiment, in the chemical formulas 1-1 to 1-3, T1 is *-N(Z 11 )(Z 12 ) or *-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - and Z 11 and Z 12 Neither is hydrogen.

[0065] According to still another embodiment, in the chemical formulas 1-1 to 1-3, T1 is *-[N(Z 11 )(Z 12 )(Z 13 )] + [Z 14 ] - and Z 11 ~Z 13 Neither is hydrogen.

[0066] According to still another embodiment, in the chemical formulas 1-1 to 1-3, T1 is a group represented by the chemical formula AN, and Z in T2 of the chemical formula AN 11 and Z 12 is hydrogen.

[0067] According to still another embodiment, in the chemical formulas 1-1 to 1-3, T1 is a group represented by the chemical formula AN, and Z in T2 of the chemical formula AN 11 is not hydrogen.

[0068] According to still another embodiment, in the chemical formulas 1-1 to 1-3, T1 is a group represented by the chemical formula AN, and in the chemical formula AN, T2 is *-[N(Z 11 )(Z 12 )] + [Z 14 ] - -*' and Z 11 and Z 12 Neither is hydrogen.

[0069] According to yet another embodiment, Z in T2 of Formula 1-4 11 and Z 12 is hydrogen.

[0070] According to yet another embodiment, Z in T2 of Formula 1-4 11 is not hydrogen, but Z 12 is hydrogen.

[0071] According to yet another embodiment, in Formula 1-4, T2 is *-[N(Z 11 )(Z 12 )] + [Z 14 ] - -*' and Z 11 and Z 12 Neither is hydrogen.

[0072] In the above chemical formulas 1-3, 1-4, AN and BN, c1 represents the number of R1 and is selected from integers of 0 to 10. When c1 is 2 or more, the two or more R1 may be the same or different.

[0073] According to yet another embodiment, in Formula 1-3, CY1 is 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.

[0074] According to still another embodiment, in Formula 1-4, ring CY2 is a saturated cyclic group having 4, 5, 6 or 7 carbon atoms.

[0075] According to yet another embodiment, in the formula AN: i)T2 is *-N(Z 11 )-*', and ring CY3 is a pyrrole group, an imidazole group, a pyrazole group, an aziridine group, an azetidine group, a pyrrolidine group, or a piperidine group, or ii) T2 is *-[N(Z 11 )(Z 12 )] + [Z 14 ] - -*', and ring CY3 is a saturated cyclic group having 4, 5, 6 or 7 carbon atoms.

[0076] According to yet another embodiment, in formula BN, ring CY4 is a pyrrole group, an imidazole group, a pyrazole group, an aziridine group, an azetidine group, a pyrrolidine group, or a piperidine group.

[0077] The R1 and R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , Z 11 , Z 12 and Z 13 are independent of each other, 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)(Q3)] +[Q4], or *-(O-CH2CH2) n1 -OH; or Deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 11 , *-NH-C(=O)-Q 11 , *-C(=O)-OQ 11 , *-SO2-Q 11 , *-P(=O)-(Q 11 )(Q 12 ), *-N(Q 11 )(Q 12 ), *-[N(Q 11 )(Q 12 )(Q 13 )] + [Q 14 ], *-(O-CH2CH2) n2 -OH, C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C2-C 30 Alkenyl groups, C3-C 30 carbocyclic group, C1-C 30 heterocyclic groups, or any combination thereof, substituted or unsubstituted, C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C2-C 30 Alkenyl groups, C3-C 30 Carbocyclic group, or C1-C 30 a heterocyclic group;

[0078] The n1 and n2 are each independently an integer of 1 to 20, for example, an integer of 1 to 10, 1 to 6, or 1 to 3.

[0079] The R1 and R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , Z 11 , Z 12 and Z 13 two or more of which can optionally be bonded to each other to form a cyclic group having 2 to 10 carbon atoms; The above Q1 to Q3 and Q11 ~Q 13 are independent of each other, 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 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, C2-C 30 Alkenyl groups, C3-C 30 carbocyclic group, C1-C 30 heterocyclic groups, or any combination thereof, substituted or unsubstituted, C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C2-C 30 Alkenyl groups, C3-C 30 Carbocyclic group, or C1-C 30 a heterocyclic group;

[0080] Said C3-C 30 Examples of carbocyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, and naphthyl groups.

[0081] Said C1-C 30 Examples of the heterocyclic group include an oxiranyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, a pyridinyl group, and a pyrimidinyl group.

[0082] Said [Z14 ] - , [Q4] - and [Q 14 ] - Each is an anion.

[0083] For example, the above [Z 14 ] - , [Q4] - and [Q 14 ] - are independently of each other: hydroxide([OH] - ), borate ([B(OH)4] - ), fluoride ([F] - ), chloride ([Cl] - ), bromide ([Br] - ), iodide([I] - ), hydrogen sulfate ([HSO4] - ), nitrate([NO3] - ), formate([HCOO] - ), acetate ([CH3COO] - ), or dihydrogen phosphate ([H2PO4] - )

[0084] In this specification, each * and *' is a bond site to the adjacent atom unless otherwise defined.

[0085] According to one embodiment, the repeating unit represented by Chemical Formula 1-3 is a repeating unit represented by one of the following Chemical Formulas 1-3(1) to 1-3(8): [ka]

[0086] In the chemical formulas 1-3(1) to 1-3(8), A1, a1, b1, T1, R1, R 14 and R 15 The explanations regarding are the same as those described in this specification, c11 is 0 or 1, c13 is an integer from 0 to 3, c15 is an integer from 0 to 5, c17 is an integer from 0 to 7, c19 is an integer from 0 to 9, * and *' are each bond sites with adjacent atoms.

[0087] According to still another embodiment, the repeating unit represented by the chemical formula 1-4 is a repeating unit represented by one of the following chemical formulas 1-4(1) to 1-4(3): [ka]

[0088] In the chemical formulas 1-4(1) to 1-4(3), b1, R1, R 14 , R 15 and T2 are the same as those described in this specification, c16 is an integer from 0 to 6, c18 is an integer from 0 to 8, * and *' are each bond sites with adjacent atoms.

[0089] According to yet another embodiment, the group represented by the chemical formula AN is a group represented by one of the following chemical formulas AN(1) to AN(12): [ka] .

[0090] In the chemical formulas AN(1) to AN(12), The descriptions of R1 and T2 are the same as those described in this specification, c12 is an integer from 0 to 2, c13 is an integer from 0 to 3, c16 is an integer from 0 to 6, c18 is an integer from 0 to 8, * indicates a bonding site with an adjacent atom.

[0091] According to yet another embodiment, the group represented by the chemical formula BN is a group represented by one of the following chemical formulas BN(1) to BN(7): [ka] .

[0092] In the chemical formulas BN(1) to BN(7), The description of R1 is the same as that described in this specification, c13 is an integer from 0 to 3, c14 is an integer from 0 to 4, c16 is an integer from 0 to 6, c18 is an integer from 0 to 8, c20 is an integer from 0 to 10, * indicates a bonding site with an adjacent atom.

[0093] According to one embodiment, the polymer having nitrogen-containing repeating units is a homopolymer (such as, for example, polymer P1).

[0094] According to another embodiment, the polymer having nitrogen-containing repeating units is a copolymer, which may be an alternating copolymer, a block copolymer, a random copolymer, or a graft copolymer.

[0095] According to yet another embodiment, the polymer having a nitrogen-containing repeating unit may also be a copolymer (e.g., polymer C1) containing a combination of two or more different nitrogen-containing repeating units as the nitrogen-containing repeating unit. According to yet another embodiment, the copolymer may contain only the combination of two or more different nitrogen-containing repeating units as the repeating unit. According to yet another implementation, the polymer having a nitrogen-containing repeating unit is a copolymer having different first and second nitrogen-containing repeating units. For descriptions of the first and second nitrogen-containing repeating units, see the descriptions of the nitrogen-containing repeating units described herein. For example, although the first and second nitrogen-containing repeating units are different from each other, the first and second nitrogen-containing repeating units may be selected from the repeating units represented by Chemical Formula 1-1, 1-2, 1-3, and 1-4 described herein. According to yet another embodiment, the copolymer may contain only the first and second nitrogen-containing repeating units.

[0096] In yet another example, the polymer having the nitrogen-containing repeating unit is a copolymer that further includes an additional repeating unit different from the nitrogen-containing repeating unit (e.g., polymer C4), which may not belong to the nitrogen-containing repeating units described herein.

[0097] According to one embodiment, the additional repeating units include repeating units derived from an ether-containing compound, repeating units derived from an alkene-containing compound, repeating units derived from a sulfur dioxide-containing compound, repeating units derived from a phosphoric acid-containing compound, repeating units derived from an amide-containing compound, repeating units derived from a carboxylic acid-containing compound, or any combination thereof.

[0098] According to another embodiment, the additional repeating unit includes a repeating unit represented by the following Formula 2-1, a repeating unit represented by the following Formula 2-2, a repeating unit represented by the following Formula 2-3, a repeating unit represented by the following Formula 2-4, a repeating unit represented by the following Formula 2-5, a repeating unit represented by the following Formula 2-6, or any combination thereof: [ka] .

[0099] In chemical formulas 2-1 to 2-6, R 21 ~R 24 are independent of each other, 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 Deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 31 , *-NH-C(=O)-Q 31 , *-C(=O)-OQ 31 , *-SO2-Q 31 , *-P(=O)-(Q 31 )(Q 32 ), *-N(Q 31 )(Q 32 ), C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C2-C 30 Alkenyl groups, C3-C 30 carbocyclic group, C1-C 30 heterocyclic groups, or any combination thereof, substituted or unsubstituted, C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C2-C 30 Alkenyl groups, C3-C 30Carbocyclic group, or C1-C 30 a heterocyclic group; Q 21 , Q 22 , Q 31 and Q 32 are independent of each other, 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 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, C2-C 30 Alkenyl groups, C3-C 30 carbocyclic group, C1-C 30 heterocyclic groups, or any combination thereof, substituted or unsubstituted, C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C2-C 30 Alkenyl groups, C3-C 30 Carbocyclic group, or C1-C 30 a heterocyclic group; d1 to d4 are each independently an integer of 0 to 20 (for example, an integer of 0 to 10), but d1+d2 is 1 or more; d5 is an integer from 1 to 20 (e.g., an integer from 1 to 20), * and *' are each bond sites with adjacent atoms.

[0100] For example, the R 21 and R 22are independent of each other, 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 Deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q 31 , *-NH-C(=O)-Q 31 , *-C(=O)-OQ 31 , *-SO2-Q 31 , *-P(=O)-(Q 31 )(Q 32 ), *-N(Q 31 )(Q 32 ), C1-C 10 C1-C substituted or unsubstituted alkyl groups, or any combination thereof 10 an alkyl group; Q 21 , Q 22 , Q 31 and Q 32 are independent of each other, Hydrogen, *-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 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 10C1-C substituted or unsubstituted alkyl groups, or any combination thereof 10 an alkyl group;

[0101] In the copolymer, the molar ratio of the nitrogen-containing repeating unit to the additional repeating unit is 1:99 to 99:1, 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, or 40:60 to 60:40.

[0102] The weight-average molecular weight of the nitrogen-containing repeating unit-containing polymer is 200 g / mol to 100,000 g / mol, for example, 400 g / mol to 10,000 g / mol, 500 g / mol to 5,000 g / mol, 600 g / mol to 3,000 g / mol, 700 g / mol to 2,500 g / mol, or 1,000 g / mol to 2,000 g / mol. The weight-average molecular weight can be measured, for example, by gel permeation chromatography (GPC), and is a calculated value using polystyrene.

[0103] The selective etching inhibitor may contain a polymer having one kind of nitrogen-containing repeating unit, or may contain a polymer having two or more kinds of nitrogen-containing repeating units. For example, the selective etching inhibitor may contain only Polymer 1, which will be described later, as the polymer having a nitrogen-containing repeating unit, or may contain a mixture of Polymer 1 and Polymer 2.

[0104] According to yet another embodiment, the polymer having nitrogen-containing repeating units is one of the following polymers 1-310 and C1-C14: [ka]

[0105] [ka]

[0106] [ka]

[0107]

change

[0108]

change

[0109]

change

[0110]

change

[0111]

change

[0112]

change

[0113]

change

[0114]

change

[0115]

change

[0116]

change

[0117] [ka]

[0118] [ka]

[0119] [ka]

[0120] [ka]

[0121] [ka] .

[0122] In the polymers 1 to 310 and C1 to C14, OMe is a methoxy group, Ph is a phenyl group, PEG is a polyethylene glycol group (*-(O-CH2-CH2) n1 —OH) (wherein n1 is an integer of 1 to 20, for example, 2 to 10, or 3 to 6), Ts is a toluenesulfonyl group (*-S(=O)2-(C6H4)-CH3), Ms is a methylsulfonyl group (*-S(=O)2-CH3), n and o are independently selected from 2 to 10,000; Each * and *' is a bonding site with an adjacent atom.

[0123] Each of the polymers 1-310 and C1-C14 can have a weight average molecular weight range as described herein.

[0124] Alternatively, the polymer having a nitrogen-containing repeating unit may be an allylamine maleic acid copolymer, a diallyldimethyl-ammonium chloride sulfur dioxide copolymer, a diallylamine sulfur dioxide copolymer, a diallylamine hydrochloride sulfur dioxide copolymer, a diallylmethylethyl-ammonium diethyl sulfate sulfur dioxide copolymer, a diallylamine acetate sulfur dioxide copolymer, a methyldiallylamine hydrochloride sulfur dioxide copolymer, a diallylamine acrylamide copolymer, a diallylamine hydrochloride acrylamide copolymer, or a diallylamine hydrochloride acrylamide copolymer. The polymers may include, for example, a methyldiallylamine maleate copolymer, a diallylamine dimethyl-ammonium chloride acrylamide copolymer, a diallylamine maleate copolymer, a diallylamine hydrochloride maleate copolymer, a diallylamine amidosulfate maleate copolymer, a methyldiallylamine maleate copolymer, a diallylmethylethyl-ammonium diethylsulfate maleate copolymer, a diallyldimethylammonium chloride maleate copolymer, a diallylamine maleate sulfur dioxide copolymer, a diallyldimethylammonium chloride maleate sulfur dioxide copolymer, or any combination thereof. Each of the polymers may have a weight average molecular weight range as described herein.

[0125] The content (weight) of the nitrogen-containing repeating unit-containing polymer is, for example, 0.001 wt% to 20 wt%, 0.001 wt% to 15 wt%, 0.001 wt% to 10 wt%, 0.001 wt% to 7 wt%, 0.001 wt% to 5 wt%, 0.001 wt% to 4 wt%, 0.001 wt% to 3 wt%, 0.001 wt% to 2 ... 01wt%~1wt%, 0.001wt%~0.5wt%, 0.001wt%~0.1wt%, 0.005wt%~20wt%, 0.005wt%~15wt%, 0.005wt%~10wt%, 0.00 5wt%~7wt%, 0.005wt%~5wt%, 0.005wt%~4wt%, 0.005wt%~3wt%, 0.005wt%~2wt%, 0.005wt%~1wt%, 0.005wt%~0.5w t%, 0.005wt%~0.1wt%, 0.01wt%~20wt%, 0.01wt%~15wt%, 0.01wt%~10wt%, 0.01wt%~7wt%, 0.01wt%~5wt%, 0.01w t%~4wt%, 0.01wt%~3wt%, 0.01wt%~2wt%, 0.01wt%~1wt%, 0.01wt%~0.5wt%, 0.01wt%~0.1wt%, 0.05wt%~20wt%, 0. 0.05wt%~15wt%, 0.05wt%~10wt%, 0.05wt%~7wt%, 0.05wt%~5wt%, 0.05wt%~4wt%, 0.05wt%~3wt%, 0.05wt%~2wt%, 0.05wt%~1wt%, 0.05wt%~0.5wt%, 0.05wt%~0.1wt%, 0.06wt%~0.4wt%, 0.07wt%~0.3wt%, or 0.075wt%~0.2wt%.

[0126] Ammonium compounds contained in selective etching inhibitors The selective etch inhibitor comprises an ammonium compound.

[0127] The ammonium compound can protect at least a portion of the surface of the metal-containing film through electrostatic attraction. For example, because the ammonium compound has a small molecular size relative to the polymer having a nitrogen-containing repeating unit, it can effectively reach the surface area of ​​the metal-containing film that is not protected by the polymer (e.g., the area between the polymers), thereby more effectively protecting the metal-containing film. Furthermore, because the ammonium compound can be easily removed later, the use of the ammonium compound can efficiently perform a metal-containing film treatment method.

[0128] The ammonium compound may include a cation and an anion.

[0129] According to one embodiment, the ammonium compound is [N(X1)(X2)(X3)(X4)] + wherein X1 to X4 are each independently hydrogen or C1-C 20 For example, X1 to X4 are each independently hydrogen or a C1-C 10 In yet another example, each of X1 to X4 is hydrogen.

[0130] According to another embodiment, the ammonium compound is NH 4+ Contains cations.

[0131] According to yet another embodiment, the ammonium compound comprises an anion, and the anion is F - , Cl - , Br - , I - , [OH] - , [(R 10 )CO2] - , [CO3] 2- , [NO3] - , [SO4] 2- , [(R 10 )SO4] - , [(R 10 )SO3] - , [C6H7O7] -, [C6H6O7] 2- , [C6H5O7] 3- , [PO3] 3- , [SO3] 2- , [C2O4] 2- , [C4H4O6] 2- , [C5H8NO4] - , [C7H5O3] - , [BF4] - , or any combination thereof.

[0132] Here, the R 10 teeth, hydrogen, deuterium, *-OH, *-SH, or *-NH2; or Deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-NH2, *-C(=O)-OH, C1-C 20 Alkyl groups, C1-C 20 C1-C substituted or unsubstituted alkoxy groups, or any combination thereof 20 Alkyl groups (e.g., C1-C 10 alkyl group), C2-C 20 Alkenyl groups (e.g., C2-C 10 alkenyl group), C1-C 20 Alkoxy groups (e.g., C1-C 10 alkoxy group), C6-C 20 Aryl groups (e.g., phenyl, naphthyl, etc.), or C2-C 20 heteroaryl groups (eg, pyridinyl groups, etc.);

[0133] According to yet another embodiment, the anion is Cl - , [OH] - , [(R 10 )CO2] - , [NO3] - , [SO4] 2- , or [(R 10 )SO3] - and R 10 teeth, hydrogen, deuterium, *-OH, *-SH, or *-NH2; or Deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-NH2, *-C(=O)-OH, C1-C 10 Alkyl groups, C1-C 10 C1-C substituted or unsubstituted alkoxy groups, or any combination thereof 10 an alkyl group;

[0134] According to yet another embodiment, the anion is F - , Cl - , Br - , I - , hydroxide, acetic acid, bicarbonate, benzoic acid, carbonic acid, formic acid, nitric acid, sulfuric acid, hydrogen sulfate, carbamic acid, trifluoroacetic acid, sulfamic acid, trifluoromethanesulfonic acid, citric acid, phosphoric acid, sulfurous acid, sulfobenzoic acid, oxalic acid, lactic acid, tartaric acid, dihydrogen citrate, glutamic acid, salicylic acid, bisoxalic acid, octanoic acid, propionic acid, glycolic acid, tetrafluoroboric acid, gluconic acid, or any combination thereof.

[0135] According to yet other embodiments, the ammonium compound comprises ammonium fluoride, ammonium chloride, ammonium hydroxide, ammonium acetate (or ammonium acetate), ammonium bicarbonate, ammonium benzoate, ammonium carbonate, ammonium formate, ammonium nitrate, ammonium sulfate, ammonium hydrogen sulfate, ammonium carbamate, ammonium trifluoroacetate, ammonium sulfamate, ammonium trifluoromethanesulfonate, diammonium citrate, triammonium citrate, triammonium phosphate, ammonium sulfite, ammonium 2-sulfobenzoic acid salt, ammonium oxalate monohydrate, ammonium lactate, ammonium tartrate, ammonium dihydrogen citrate, L-glutamic acid monoammonium salt, ammonium salicylate, ammonium bisoxalate monohydrate, ammonium octanoate, ammonium propionate, ammonium glycolate, ammonium tetrafluoroborate, ammonium gluconate, or any combination thereof.

[0136] The content (weight) of the ammonium salt is, for example, 0.001 wt% to 20 wt%, 0.001 wt% to 15 wt%, 0.001 wt% to 10 wt%, 0.001 wt% to 7 wt%, 0.001 wt% to 5 wt%, 0.001 wt% to 4 wt%, 0.001 wt% to 5 ... ~3wt%, 0.001wt%~2wt%, 0.001wt%~1wt%, 0.01wt%~20wt%, 0.01wt%~15wt%, 0.0 1wt%~10wt%, 0.01wt%~7wt%, 0.01wt%~5wt%, 0.01wt%~4wt%, 0.01wt%~3wt%, 0.0 1wt%~2wt%, 0.01wt%~1wt%, 0.05wt%~20wt%, 0.05wt%~15wt%, 0.05wt%~10wt%, 0.05wt%~7wt%, 0.05wt%~5wt%, 0.05wt%~4wt%, 0.05wt%~3wt%, 0.05wt%~2wt%, 0 0.05wt%~1wt%, 0.02wt%~1.5wt%, 0.03wt%~1.3wt%, 0.04wt%~1.2wt%, 0.1wt%~1.1wt%, 0.2wt%~1wt%, 0.3wt%~0.9wt%, 0.4wt%~0.8wt%, or 0.5wt%~0.7wt%.

[0137] The weight ratio of the polymer having a nitrogen-containing repeating unit (based on solid content) to the ammonium compound is 1:0.01 to 1:50, 1:0.1 to 1:30, or 1:0.1 to 1:15. When the weight ratio of the polymer having a nitrogen-containing repeating unit to the ammonium compound satisfies the above range, the etching rate of the metal-containing film can be effectively controlled.

[0138] The selective etch inhibitor may further include an amine-containing compound other than the polymer having a nitrogen-containing repeating unit and the ammonium compound. By including the amine-containing compound, the etch rate and etch selectivity for the metal-containing film can be effectively controlled.

[0139] According to one embodiment, the amine-containing compound comprises an alkylamine, an alkanolamine, or any combination thereof.

[0140] According to other embodiments, the amine-containing compound comprises a monoalkylamine (e.g., monobutylamine), a monoalkanolamine (e.g., ethanolamine), or any combination thereof.

[0141] According to yet another embodiment, the amine-containing compound comprises a compound represented by Formula 5: [Chemical formula 5] N(Q 51 )(Q 52 )(Q 53 ) In the above Chemical Formula 5, Q 51 ~Q 53 are independent of each other, 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 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, C2-C 30 Alkenyl groups, C3-C 30 carbocyclic group, C1-C 30 heterocyclic groups, or any combination thereof, substituted or unsubstituted, C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C2-C30 Alkenyl groups, C3-C 30 Carbocyclic group, or C1-C 30 Heterocyclic group; but Q 51 ~Q 53 At least one of them is not hydrogen.

[0142] For example, in the above Chemical Formula 5, Q 51 ~Q 53 are independent of each other, hydrogen; or *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH2, *-C(=O)-NH(CH3), *-C(=O)-N(C H3)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, C2-C 30 Alkenyl groups, C3-C 30 carbocyclic group, C1-C 30 heterocyclic groups, or any combination thereof, substituted or unsubstituted, 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 group; but Q 51 ~Q 53 At least one of them is not hydrogen.

[0143] As another example, in the above Chemical Formula 5, Q 51 and Q 52 is hydrogen and Q 53 is C1-C 20 alkyl groups; or C1-C substituted with -F, -OH, or any combination thereof 20 an alkyl group;

[0144] When the selective etching inhibitor further comprises an amine-containing compound, the weight ratio of the polymer having a nitrogen-containing repeating unit to the amine-containing compound is 1:0.01 to 1:10.

[0145] The content (weight) of the selective etching inhibitor per 100 wt% of the composition is, for example, 0.001 wt% to 20 wt%, 0.001 wt% to 15 wt%, 0.001 wt% to 10 wt%, 0.001 wt% to 7 wt%, 0.001 wt% to 5 wt%, 0.001 wt% to 4 wt%, 0.001 wt% to 3 wt%, 0.001 wt% to 2 wt%, 0.001 wt% to 1.5 wt%, 0.01 wt% to 20 wt%, 0.01 wt% to 15 wt%, 0.01 wt% % to 10 wt%, 0.01 wt% to 7 wt%, 0.01 wt% to 5 wt%, 0.01 wt% to 4 wt%, 0.01 wt% to 3 wt%, 0.01 wt% to 2 wt%, 0.01 wt% to 1.5 wt%, 0.1 wt% to 20 wt%, 0.1 wt% to 15 wt%, 0.1 wt% to 10 wt%, 0.1 wt% to 7 wt%, 0.1 wt% to 5 wt%, 0.1 wt% to 4 wt%, 0.1 wt% to 3 wt%, 0.1 wt% to 2 wt%, or 0.1 wt% to 1.5 wt%, where the content of the polymer having a nitrogen-containing repeating unit contained in the selective etching inhibitor is evaluated based on the solid content.

[0146] According to one embodiment, in the composition, the content of the oxidizing agent is 0.5 wt% to 20 wt% per 100 wt% of the composition, the content of the acid is 30 wt% to 80 wt% per 100 wt% of the composition, and the content of the selective etching inhibitor is 0.01 wt% to 2 wt% per 100 wt% of the composition.

[0147] The composition may have a pH of 1.0 to 8.0, 1.0 to 7.0, 1.0 to 6.0, 1.0 to 5.0, 1.0 to 4.0, 1.0 to 3.0, 2.0 to 8.0, 2.0 to 7.0, 2.0 to 6.0, 2.0 to 5.0, 2.0 to 4.0, 2.0 to 3.0, 3.0 to 8.0, 3.0 to 7.0, 3.0 to 6.0, 3.0 to 5.0, 3.0 to 4.0, 4.0 to 8.0, 4.0 to 7.0, 4.0 to 6.0, 4.0 to 5.0, 5.0 to 8.0, 5.0 to 7.0, or 5.0 to 6.0. When the composition has a pH within the above range, the interaction between the selective etching inhibitor and the metal atoms in the metal-containing film may be more smoothly carried out.

[0148] In one embodiment, the composition can be used in metal-containing film processing steps, such as etching, cleaning, and polishing steps for metal-containing films, as described herein.

[0149] Alternatively, the composition can be used as an etching by-product remover, a post-etch 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 wafer adhesive material remover, an etchant, a post-etch residue stripper, an ash residue cleaner, a photoresist (PR) residue stripper, a polishing (CMP) cleaner, or a post-CMP cleaner.

[0150] METHOD FOR PROCESSING METAL-CONTAINING FILM AND METHOD FOR PRODUCING SEMICONDUCTOR DEVICE Compositions such as those described above can be used to effectively treat metal-containing films.

[0151] Referring to FIG. 1, one embodiment of the method for treating a metal-containing film includes the steps of: preparing a substrate having a metal-containing film provided thereon (S100); and contacting the metal-containing film with a composition described herein (S110).

[0152] For a description of the metal-containing film, please refer to the description herein.

[0153] For example, the metal included in the metal-containing film may include titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

[0154] As yet another example, the metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.

[0155] In yet another example, the metal-containing film includes titanium nitride.

[0156] In yet another example, the metal-containing film includes tungsten.

[0157] According to one embodiment, contacting the metal-containing film with the composition may etch, clean, or polish one or more portions of the metal-containing film.

[0158] The composition contains the selective etching inhibitor containing both the polymer having a nitrogen-containing repeating unit and an ammonium compound, as described above, and therefore the etching rate for various metal-containing films can be easily controlled.

[0159] Meanwhile, referring to FIG. 1, a method for manufacturing a semiconductor device according to one embodiment includes a step of preparing a substrate having a metal-containing film provided thereon (S100), a step of contacting the metal-containing film with the composition (S110), and a step of fabricating a semiconductor device by performing subsequent processes (S120).

[0160] Examples 1 to 5 and Comparative Examples A and B Compositions of Examples 1 to 5 and Comparative Examples A and B were prepared by mixing 4 wt% hydrogen peroxide as an oxidizing agent, 70 wt% phosphoric acid as an acid, and a selective etching inhibitor listed in Tables 1 and 2. The weight-average molecular weight of polymer P1 was 1600 g / mol, and the remainder of each composition was water (deionized water).

[0161] Evaluation example 1 The compositions of Example 1 were placed in beakers and heated to 70°C. A tungsten film (W film) test piece measuring 1 cm x 1 cm was then immersed in the beaker for 5 minutes. The thickness of the tungsten film was measured using an ellipsometer (M-2000, JA Woolam), a four-point probe, and XRF to evaluate the etching rate (Å / min) of the composition of Example 1 against the tungsten film. The results are shown in Table 1.

[0162] The above test was repeated using the etching compositions of Examples 2 to 4 and Comparative Examples A and B, and the results are shown in Table 1.

[0163] [Table 1]

[0164] [ka]

[0165] From Table 1, it can be seen that the compositions of Examples 1 to 4 have superior etching suppression performance against tungsten films compared to the compositions of Comparative Examples A and B.

[0166] Evaluation example 2 The etching rates (Å / min) of the compositions of Examples 3 and 5 and Comparative Examples A and B against titanium nitride films were evaluated in the same manner as in Evaluation Example 1, except that titanium nitride film (TiN film) specimens were used instead of tungsten film (W film) specimens. The results are shown in Table 2.

[0167] [Table 2]

[0168] [ka]

[0169] From Table 2, it can be seen that the compositions of Examples 3 and 5 have superior etching suppression performance against titanium nitride films compared to the compositions of Comparative Examples A and B.

Claims

1. comprising an oxidizing agent, an acid, and a selective etch inhibitor; The selective etch inhibitor comprises a polymer having a nitrogen-containing repeating unit and an ammonium compound.

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

3. The composition of claim 1 , wherein the acid comprises phosphoric acid.

4. The composition of claim 1, wherein the nitrogen-containing repeating unit comprises a repeating unit represented by the following chemical formula 1-1, a repeating unit represented by the following chemical formula 1-2, a repeating unit represented by the following chemical formula 1-3, a repeating unit represented by the following chemical formula 1-4, or any combination thereof: 【Chemical 1】 In Chemical Formulas 1-1 to 1-3, A １ is *-C(R １６ ) (R １７ )-*', *-N(R １６ )-*', *-C(=O)-*', *-O-*', or *-S-*'; In Chemical Formulas 1-1 to 1-3, a1 is an integer of 0 to 20, and when a1 is 2 or more, A １ may be the same or different from each other, In Chemical Formulas 1-1 to 1-4, b1 is an integer of 0 to 10, and when b1 is 2 or more, two or more *-C(R １４ ) (R １５ )-*' may be the same or different, In Chemical Formulas 1-1 to 1-3, T １ is *-N(Z １１ ) (Z １２ ), *-[N(Z １１ ) (Z １２ ) (Z １３ )] ＋ [Z １４ ] － , a group represented by the following chemical formula AN, or a group represented by the following chemical formula BN, 【Chemistry 2】 In the above chemical formulas 1-3, 1-4, AN and BN, the ring CY １ ~ Tamaki CY ４ are each independently a cyclic group having 2 to 10 carbon atoms, In the formulas 1-3, 1-4, AN, and BN, c1 is selected from integers of 0 to 10, and when c1 is 2 or more, two or more R １ may be the same or different from each other, In the above formulas 1-4 and AN, T ２ is *-N(Z １１ )-*' or *-[N(Z １１ ) (Z １２ )] ＋ [Z １４ ] － -*', The R １ , R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ , Z １１ , Z １２ and Z １３ are independent of each other, Hydrogen, deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q １ , *-NH-C(=O)-Q １ , *-C(=O)-O-Q 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 Deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-Q １１ , *-NH-C(=O)-Q １１ , *-C(=O)-O-Q １１ , *-SO ２ -Q １１ , *-P(=O)-(Q １１ ) (Q １２ ), *-N(Q １１ ) (Q １２ ), *-[N(Q １１ ) (Q １２ ) (Q １３ )] ＋ [Q １４ ] － , *-(O-CH ２ CH ２ ) ｎ２ -OH, C １ -C ３０ Alkyl group, C １ -C ３０ Alkoxy group, C ２ -C ３０ Alkenyl group, C ３ -C ３０ Carbocyclic group, C １ -C ３０ C, substituted or unsubstituted with heterocyclic groups, or any combination thereof １ -C ３０ Alkyl group, C １ -C ３０ Alkoxy group, C ２ -C ３０ Alkenyl group, C ３ -C ３０ a carbocyclic group, or C １ -C ３０ a heterocyclic group; n1 and n2 are each independently an integer of 1 to 20, The R １ , R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ , Z １１ , Z １２ and Z １３ two or more of which may optionally be bonded to each other to form a cyclic group having 2 to 10 carbon atoms; Q １ ~Q ３ and Q １１ ~Q １３ are independent of each other, 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 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 group, C ２ -C ３０ Alkenyl group, C ３ -C ３０ Carbocyclic group, C １ -C ３０ C, substituted or unsubstituted with heterocyclic groups, or any combination thereof １ -C ３０ Alkyl group, C １ -C ３０ Alkoxy group, C ２ -C ３０ Alkenyl group, C ３ -C ３０ a carbocyclic group, or C １ -C ３０ a heterocyclic group; [Z １４ ] － , [Q ４ ] － and [Q １４ ] － Each is an anion, Each of * and *' is a bonding site with an adjacent atom.

5. In the above formula 1-3, CY １ The composition of claim 4 , wherein is 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.

6. In the above Chemical Formula 1-4, the ring CY ２ The composition of claim 4, wherein is a saturated cyclic group having 4, 5, 6 or 7 carbon atoms.

7. In the above chemical formula AN, i) T ２ is *-N(Z １１ )-*', and the ring CY ３ is a pyrrole group, an imidazole group, a pyrazole group, an aziridine group, an azetidine group, a pyrrolidine group, or a piperidine group; ii) T ２ is *-[N(Z １１ ) (Z １２ )] ＋ [Z １４ ] － -*' and the ring CY ３ The composition of claim 4 , wherein is a saturated cyclic group having 4, 5, 6, or 7 carbon atoms.

8. In the formula BN, the ring CY ４ The composition of claim 4 , wherein is a pyrrole group, an imidazole group, a pyrazole group, an aziridine group, an azetidine group, a pyrrolidine group, or a piperidine group.

9. The composition of claim 1 wherein the polymer having nitrogen-containing repeating units is a homopolymer.

10. i) the polymer having a nitrogen-containing repeating unit is a copolymer containing, as the nitrogen-containing repeating unit, a combination of two or more different nitrogen-containing repeating units, or ii) The composition of claim 1, wherein the polymer having the nitrogen-containing repeating unit is a copolymer further comprising, in addition to the nitrogen-containing repeating unit, an additional repeating unit different from the nitrogen-containing repeating unit.

11. The ammonium compound is [N(X １ ) (X ２ ) (X ３ ) (X ４ )] ＋ The X １ ~X ４ are independently hydrogen or C １ -C ２０ The composition of claim 1 , wherein the alkyl group is an alkyl group.

12. the ammonium compound comprises an anion; The anion is F － , Cl － ,Br － , I － , [OH] － , [(R １０ ) CO ２ ] － , [CO ３ ] ２－ , [NO ３ ] － , [SO ４ ] ２－ , [(R １０ ) SO ４ ] － , [(R １０ ) SO ３ ] － , [C ６ H ７ O ７ ] － , [C ６ H ６ O ７ ] ２－ , [C ６ H ５ O ７ ] ３－ , [PO ３ ] ３－ , [SO ３ ] ２－ , [C ２ O ４ ] ２－ , [C ４ H ４ O ６ ] ２－ , [C ５ H ８ NO ４ ] － , [C ７ H ５ O ３ ] － , [B.F. ４ ] － or any combination thereof, The R １０ but, Hydrogen, deuterium, *-OH, *-SH, or *-NH ２ ;or Deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-NH ２ , *-C(=O)-OH, C １ -C ２０ Alkyl group, C １ -C ２０ substituted or unsubstituted with alkoxy groups, or any combination thereof, １ -C ２０ Alkyl group, C ２ -C ２０ Alkenyl group, C １ -C ２０ Alkoxy group, C ６ -C ２０ an aryl group, or C ２ -C ２０ 2. The composition of claim 1, wherein:

13. 2. The composition of claim 1, wherein the ammonium compound comprises ammonium fluoride, ammonium chloride, ammonium hydroxide, ammonium acetate (or ammonium acetate), ammonium bicarbonate, ammonium benzoate, ammonium carbonate, ammonium formate, ammonium nitrate, ammonium sulfate, ammonium hydrogen sulfate, ammonium carbamate, ammonium trifluoroacetate, ammonium sulfamate, ammonium trifluoromethanesulfonate, diammonium citrate, triammonium citrate, triammonium phosphate, ammonium sulfite, ammonium 2-sulfobenzoic acid salt, ammonium oxalate monohydrate, ammonium lactate, ammonium tartrate, ammonium dihydrogen citrate, L-glutamic acid monoammonium salt, ammonium salicylate, ammonium bisoxalate monohydrate, ammonium octanoate, ammonium propionate, ammonium glycolate, ammonium tetrafluoroborate, ammonium gluconate, or any combination thereof.

14. 2. The composition of claim 1, wherein the content of the selective etching inhibitor is 0.001 wt % to 20 wt % per 100 wt % of the composition.

15. The content of the oxidizing agent is 0.5 wt % to 20 wt % per 100 wt % of the composition; The content of the acid is 30 wt % to 80 wt % per 100 wt % of the composition; 2. The composition of claim 1, wherein the content of the selective etching inhibitor is 0.01 wt % to 2 wt % per 100 wt % of the composition.

16. providing a substrate having a metal-containing film provided thereon; and contacting the metal-containing film with the composition of any one of claims 1 to 15.

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

18. 17. The method of treating a metal-containing film of claim 16, wherein the metal-containing film comprises a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.

19. 17. The method of treating a metal-containing film of claim 16, wherein contacting the metal-containing film with the composition etches, cleans, or polishes at least a portion of the metal-containing film.

20. providing a substrate having a metal-containing film provided thereon; contacting the metal-containing film with the composition of any one of claims 1 to 15; and performing subsequent manufacturing process(es) to fabricate a semiconductor device.

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