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

Abstract

Provided are an etching composition, a method of etching a metal-containing layer using the same, and a method of manufacturing a semiconductor device using the same. The etching composition includes a hypervalent iodine-containing compound.

Description

[0001] Cross - reference to related applications

[0002] This application is based on and claims priority to Korean Patent Application No. 10 - 2023 - 0195609, filed with the Korean Intellectual Property Office on December 28, 2023, the entire disclosure of which is incorporated herein by reference. Technical Field

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

[0004] To meet customers' demands for excellent performance and low price, improvement in the integration and reliability of semiconductor devices has been required. As the integration degree of semiconductor devices increases, during the process of manufacturing semiconductor devices, damage to the elements of semiconductor devices has a stronger impact on the reliability and electrical characteristics of semiconductor memory devices. In particular, in the semiconductor device manufacturing process, various etching processes are performed on some layers (e.g., metal - containing layers), and there is a continuous need for an etching composition that can provide an excellent etching rate, excellent etching selectivity to adjacent layers, no post - etching residue on the surface, and excellent storage stability to effectively perform the etching process. Summary of the Invention

[0005] Provided is an etching composition that has excellent etching selectivity for a metal - containing layer as a layer to be etched and can improve the productivity and efficiency of an etching process.

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

[0007] According to one aspect of the present disclosure, the etching composition may include a hypervalent iodine - containing compound.

[0008] In some embodiments, the etching composition may further include an acid and water.

[0009] In some embodiments, the hypervalent iodine - containing compound may include trivalent iodine (iodine(III)) or pentavalent iodine (iodine(V)).

[0010] In some embodiments, the hypervalent iodine - containing compound may include iodine and one or more carbon atoms, wherein one of the carbon atoms may be bonded to the iodine via a chemical bond.

[0011] In some embodiments, the hypervalent iodine-containing compound may include iodine and n ligands bonded to the iodine, wherein at least one of the ligands may include a C1-C 30 aromatic cyclic group.

[0012] In some embodiments, the amount of the hypervalent iodine-containing compound may be from 0.005 wt% to 1 wt%, based on 100 wt% of the etching composition.

[0013] In some embodiments, the acid may include a fluorine-based inorganic acid.

[0014] In some embodiments, the amount of the acid may be from 0.0001 wt% to 20 wt%, based on 100 wt% of the etching composition.

[0015] In some embodiments, the etching composition may further include a pH regulator.

[0016] In some embodiments, the etching composition may have a pH of from 0 to 4.0.

[0017] According to another aspect of the present disclosure, a method of etching a metal-containing layer may include: preparing a substrate provided with a metal-containing layer, and performing an etching process on the metal-containing layer by using the etching composition to remove at least a portion of the metal-containing layer.

[0018] In some embodiments, the metal-containing layer may include indium (In), titanium (Ti), aluminum (Al), tungsten (W), lanthanum (La), scandium (Sc), gallium (Ga), zinc (Zn), hafnium (Hf), molybdenum (Mo), or any combination thereof.

[0019] In some embodiments, the metal-containing layer may include a first region and a second region,

[0020] In some embodiments, a second etching rate of the composition for etching the second region may be greater than a first etching rate of the composition for etching the first region, and the etching process may be performed by bringing at least a portion of the first region and at least a portion of the second region into contact with the etching composition.

[0021] In some embodiments, the first region may include molybdenum, and the second region may include titanium nitride (TiN).

[0022] According to one aspect of the present disclosure, a method of manufacturing a semiconductor device may include: preparing a substrate provided with a metal-containing layer, performing an etching process on the metal-containing layer by using the etching composition to remove at least a portion of the metal-containing layer, and performing subsequent manufacturing processes to manufacture a semiconductor device. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The above and other aspects, features, and advantages of some embodiments of the present disclosure will become more apparent from the following description considered in conjunction with the accompanying drawings, in which:

[0024] Figure 1 is a process flow diagram of a method for manufacturing a semiconductor device according to an embodiment; and

[0025] Figure 2 and 3 is a diagram for schematically describing a method for etching a metal-containing layer according to an embodiment. DETAILED DESCRIPTION

[0026] Embodiments will now be described in detail, examples of which are illustrated in the accompanying drawings, where like reference numerals always refer to like elements. In this regard, the present embodiments may have different forms and should not be construed as limited to the description set forth herein. Therefore, the embodiments are described only by way of example by referring to the accompanying drawings below. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items. When preceding or following a list of elements, expressions such as "at least one (kind) of..." modify the entire list of elements and not individual elements of the list. For example, "at least one (kind) of A, B, and C" and similar language (e.g., "selected from at least one (kind) of 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.

[0027] When the term "about" or "substantially" is used in this specification in connection with a numerical value, it is intended that the associated numerical value include manufacturing or operational tolerances around the stated numerical value (e.g., ±10%). Further, when the words "substantially" and "essentially" are used in connection with a geometric shape, it is intended that the precision of the geometric shape is not required, but the tolerance for the stated shape is within the scope of the present disclosure. Further, whether a numerical value or a shape is modified by "about" or "substantially", it will be understood that these values and shapes should be interpreted as including manufacturing or operational tolerances around the stated numerical value or shape (e.g., ±10%). When a range is specified, the range includes all values therebetween, such as increments of 0.1%.

[0028] Layer to be etched

[0029] The layer to be etched may include a metal-containing layer.

[0030] Therefore, the etching composition can be used in an etching process and / or a CMP (chemical mechanical polishing) process for a metal-containing layer.

[0031] The metal included in the metal-containing layer may include alkali metals (e.g., sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs)), alkaline earth metals (e.g., beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba)), lanthanide (lanthanum group) metals (e.g., lanthanum (La), europium (Eu), terbium (Tb), and ytterbium (Yb)), transition metals (e.g., scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), nickel (Ni), copper (Cu), silver (Ag), and zinc (Zn)), post-transition metals (e.g., aluminum (Al), gallium (Ga), indium (In), thallium (Tl), tin (Sn), and bismuth (Bi)), or any combination thereof.

[0032] According to one embodiment, the metal-containing layer may include indium (In), titanium (Ti), aluminum (Al), copper (Cu), tungsten (W), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), zinc (Zn), hafnium (Hf), molybdenum (Mo), or any combination thereof.

[0033] According to another embodiment, the metal-containing layer may include indium (In), titanium (Ti), aluminum (Al), tungsten (W), lanthanum (La), scandium (Sc), gallium (Ga), zinc (Zn), hafnium (Hf), molybdenum (Mo), or any combination thereof.

[0034] For example, the metal-containing layer may include aluminum, titanium, lanthanum, tungsten, molybdenum, or any combination thereof.

[0035] As another example, the metal-containing layer may include titanium.

[0036] As another example, the metal-containing layer may include titanium and aluminum.

[0037] As another example, the metal-containing layer may include tungsten.

[0038] As another example, the metal-containing layer may include molybdenum.

[0039] The metal-containing layer may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.

[0040] The metal-containing layer may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof, and the metal and the metals respectively included in the metal nitride, the metal oxide, and the metal oxynitride may include indium (In), titanium (Ti), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), zinc (Zn), hafnium (Hf), or any combination thereof.

[0041] The metal-containing layer may include a metal nitride. The metal included in the metal nitride may include indium, titanium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof.

[0042] As another example, the metal-containing layer may include titanium nitride. The titanium nitride may further include indium, aluminum, lanthanum, scandium, gallium, hafnium, zinc, or any combination thereof. As another example, the metal-containing layer may include titanium nitride (TiN), titanium nitride further including aluminum (e.g., titanium / aluminum nitride or TiAlN), or titanium nitride further including lanthanum.

[0043] As another example, the metal-containing layer may include a metal oxide. The metal included in the metal oxide may include titanium, aluminum, lanthanum, scandium, gallium, hafnium, or any combination thereof. For example, the metal-containing layer may include aluminum oxide (e.g., Al2O3), indium gallium zinc oxide (IGZO), etc.

[0044] As another example, the metal-containing layer may include the metal and the metal nitride.

[0045] According to another embodiment, the metal-containing film may include the metal nitride and the metal oxide.

[0046] As another example, in addition to the metal, the metal-containing layer may further include metalloids (e.g., boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te)), non-metals (e.g., nitrogen (N), phosphorus (P), oxygen (O), sulfur (S), and selenium (Se)), or any combination thereof.

[0047] For example, the metal-containing layer may further include silicon oxide.

[0048] The metal-containing layer may have a single-layer structure including one or more substances (or consisting of them), or a multi-layer or patterned structure including different substances.

[0049] For example, the metal-containing layer may have i) a single-layer structure comprising titanium nitride (or consisting thereof), ii) a bilayer or patterned structure comprising a first layer and a second layer, the first layer comprising titanium nitride (or consisting thereof), and the second layer comprising titanium nitride further comprising aluminum (or consisting thereof), iii) a bilayer or patterned structure comprising a first layer and a second layer, the first layer comprising titanium nitride (or consisting thereof), and the second layer comprising aluminum oxide (or consisting thereof), or iv) a bilayer or patterned structure comprising a first layer and a second layer, the first layer comprising titanium nitride (or consisting thereof), and the second layer comprising molybdenum (or consisting thereof).

[0050] According to another embodiment, the metal-containing layer may include a first region and a second region, and a second etching rate of the composition for etching the second region may be greater than a first etching rate of the composition for etching the first region. During an etching process and / or a polishing process of the metal-containing layer, 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 the second region may be etched faster than the first region because the second etching rate is greater than the first etching rate.

[0051] For example, the first region may include a metal, a metal oxide (e.g., aluminum oxide), silicon oxide, or any combination thereof.

[0052] According to one embodiment, the first region may include molybdenum.

[0053] As another example, the second region may include a metal nitride.

[0054] As another example, the second region may include i) titanium nitride, ii) titanium nitride further comprising indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) any combination thereof.

[0055] As another example, each of the first region and the second region may include i) titanium nitride, ii) titanium nitride further comprising indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) any combination thereof.

[0056] As another example, the first region may include aluminum and the second region may not include aluminum.

[0057] As another example, the first region may include titanium nitride further comprising aluminum (e.g., titanium / aluminum nitride or TiAlN), and the second region may include titanium nitride (TiN).

[0058] As another example, the first region may include a titanium nitride layer further including aluminum (e.g., a titanium / aluminum nitride layer or a TiAlN layer), and the second region may include a titanium nitride layer (TiN layer).

[0059] As another example, the first region may be a titanium nitride layer further including aluminum (e.g., a titanium / aluminum nitride layer or a TiAlN layer), and the second region may be a titanium nitride layer (TiN layer).

[0060] As another example, the first region may include molybdenum, and the second region may not include molybdenum.

[0061] As another example, the first region may include molybdenum, and the second region may include titanium nitride (TiN).

[0062] As another example, the first region may include a molybdenum layer (Mo layer), and the second region may include a titanium nitride layer (TiN layer).

[0063] As another example, the first region may be a molybdenum layer (Mo layer), and the second region may be a titanium nitride layer (TiN layer).

[0064] Throughout the specification, the expression "etching layer" may refer to removing at least a part of the material constituting the layer.

[0065] Etching composition

[0066] The etching composition may include a compound containing hypervalent iodine.

[0067] In addition to the compound containing hypervalent iodine, the etching composition may further include an acid, a pH regulator, a selective etching inhibitor, a selective etching promoter, a solvent, water, or any combination thereof.

[0068] For example, in addition to the compound containing hypervalent iodine, the etching composition may further include an acid and water. In a case where, in addition to the compound containing hypervalent iodine, the etching composition further includes an acid and water, the compound containing hypervalent iodine may act as an oxidizing agent.

[0069] As another example, in addition to the compound containing hypervalent iodine, the etching composition may further include a pH regulator.

[0070] As another example, in addition to the compound containing hypervalent iodine, the etching composition may further include an acid, a pH regulator, and water.

[0071] The etching composition may be used in the etching process and / or the CMP process of the layer to be etched described in this specification, such as the metal-containing layer.

[0072] Compound containing hypervalent iodine

[0073] The compound containing hypervalent iodine can be used to etch the metal-containing layer. For example, the compound containing hypervalent iodine can be used to remove titanium atoms from the metal-containing layer. As another example, the compound containing hypervalent iodine can act as an oxidizing agent.

[0074] According to one embodiment, the compound containing hypervalent iodine may include trivalent iodine (iodine(III)) or pentavalent iodine (iodine(V)).

[0075] According to another embodiment, the compound containing hypervalent iodine may include iodine and one or more carbon atoms, wherein one of the carbon atoms may be bonded to the iodine via a chemical bond.

[0076] According to another embodiment, the compound containing hypervalent iodine may include iodine and n ligands bonded to the iodine, where n may be 1, 2, 3, 4, 5, or 6 (for example, 1, 2, or 3).

[0077] According to another embodiment, among the n ligands, at least one ligand may be an organic ligand. For example, at least one of the n ligands may include a C1-C 30 aromatic cyclic group (for example, benzene group, naphthalene group, pyridine group, and pyrimidine group).

[0078] According to another embodiment, each of the n ligands may be a monodentate ligand or a bidentate ligand.

[0079] According to another embodiment, the compound containing hypervalent iodine may be a compound represented by Formula 1, a compound represented by Formula 2, a compound represented by Formula 3, a compound represented by Formula 4, or any combination thereof.

[0080] <Formula 1>

[0081] I(L1)(L2)(L3)

[0082] <Formula 2>

[0083]

[0084] <Formula 3>

[0085]

[0086] <Formula 4>

[0087]

[0088] In Formulas 1 to 4,

[0089] L1, L2, L3, and L4 are each independently a ligand bonded to the iodine of Formulas 1 to 4,

[0090] L1 and L2 are each independently *-OH, *-SH, *-O(Q1), *-S(Q1), *-O-S(=O)2-Q1, *-O-C(=O)-Q1, *-S-C(=O)-Q1, *-O-C(=S)-Q1, *-S-C(=S)-Q1, *-S(=O)2-Q1, *-C(=O)-Q1, *-C(=S)-Q1, *-S(=O)2-O-Q1, *-C(=O)-O-Q1, or *-C(=S)-O-Q1,

[0091] L3 and L4 are each independently a C3-C 30 carbocyclic group or a C1-C 30 heterocyclic group: 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, *-SO3(Q 11 ), C1-C 30 alkyl, C1-C 30 alkoxy, C2-C 30 alkenyl, C3-C 30 carbocyclic group, C1-C 30 heterocyclic group, or any combination thereof,

[0092] Ring CY2 is a C3-C 30 carbocyclic group or a C1-C 30 heterocyclic group,

[0093] Q1 and Q2 are each independently:

[0094] 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), *-N(CH3)2, or *-SO3(Q 11 ), or

[0095] a C1-C that is unsubstituted or substituted with the following 30alkyl, C1-C 30 alkoxy, C2-C 30 alkenyl, C3-C 30 carbocyclic group, or C1-C 30 heterocyclic group: 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, *-SO3(Q 11 ), C1-C 30 alkyl, C1-C 30 alkoxy, C2-C 30 alkenyl, C3-C 30 carbocyclic group, C1-C 30 heterocyclic group, or any combination thereof,

[0096] n2 is an integer from 0 to 10,

[0097] Q 11 is hydrogen or an alkali metal,

[0098] T + is [N(Q 21 )(Q 22 )(Q 23 )] + , Q 21 to Q 23 is as described above for Q1, and

[0099] * is the binding site to the adjacent atom. In other words, Q 21 to Q 23 can independently be any element or group described above for Q1.

[0100] For example, in Formula 1, L2 can be *-O-S(=O)2-Q1, *-O-C(=O)-Q1, *-S-C(=O)-Q1, *-O-C(=S)-Q1, *-S-C(=S)-Q1, *-S(=O)2-Q1, *-C(=O)-Q1, *-C(=S)-Q1, *-S(=O)2-O-Q1, *-C(=O)-O-Q1, or *-C(=S)-O-Q1, and preferably, L2 can be *-O-S(=O)2-Q1 or *-O-C(=O)-Q1.

[0101] According to one embodiment, in Formulas 1 and 3, L1 can be *-OH, *-O-S(=O)2-Q1, or *-O-C(=O)-Q1.

[0102] According to another embodiment, in Formula 1, L1 and L2 can be the same as each other.

[0103] According to another embodiment, in Formula 1, L1 and L2 can be different from each other.

[0104] According to another embodiment, in Formula 1, the bond between iodine and ligand L3 can be an iodine-carbon bond.

[0105] According to another embodiment, Q1 can be a C1-C 10 alkyl group, a C1-C 10 alkoxy group, a phenyl group, a naphthyl group, or a pyridyl group, each unsubstituted or substituted with: deuterium, *-F, a C1-C 10 alkyl group, a C1-C 10 alkoxy group, a phenyl group, a naphthyl group, a pyridyl group, or any combination thereof.

[0106] According to another embodiment, in Formula 1, L3 can be a phenyl group, a naphthyl group, or a pyridyl group, each unsubstituted or substituted with: deuterium, *-F, a C1-C 10 alkyl group, a C1-C 10 alkoxy group, a phenyl group, a naphthyl group, a pyridyl group, or any combination thereof.

[0107] According to another embodiment, in Formulas 2 and 3, ring CY2 can be a benzene group, a naphthalene group, a phenanthrene group, a pyridine group, a pyrimidine group, a pyrazine group, or a pyridazine group.

[0108] According to another embodiment, in Formulas 2 and 3, Q2 can be hydrogen, *-C(=O)-OH, or *-SO3(Q 11 ).

[0109] According to another embodiment, in Formulas 2 and 3, n2 can be 0, 1, or 2.

[0110] According to another embodiment, in Formula 4, L4 can be a phenyl group, a naphthyl group, or a pyridyl group, each unsubstituted or substituted with: deuterium, *-F, *-SO3(Q 11 ), a C1-C 10 alkyl group, a C1-C 10 alkoxy group, a phenyl group, a naphthyl group, a pyridyl group, or any combination thereof.

[0111] According to another embodiment, Q 11 can be hydrogen, Li, Na, K, Rb, or Cs.

[0112] According to another embodiment, in Formula 2, T+ It may be [N(Q 21 )(Q 22 )(Q 23 )] + , and Q 21 to Q 23 can each independently be a C1-C 10 alkyl, C1-C 10 alkoxy, phenyl, naphthyl, or pyridyl group that is unsubstituted or substituted with the following: deuterium, *-F, C1-C 10 alkyl, C1-C 10 alkoxy, or any combination thereof.

[0113] According to another embodiment, the compound represented by Formula 2 can be the compound represented by Formula 2A below, and the compound represented by Formula 3 can be the compound represented by Formula 3A below.

[0114] <Formula 2A>

[0115]

[0116] <Formula 3A>

[0117]

[0118] In Formulas 2A and 3A, L1, Q2, and T + As described above, n2 in Formula 2A is an integer from 0 to 3, and n2 in Formula 3A is an integer from 0 to 4.

[0119] According to another embodiment, the hypervalent iodine-containing compound may include the compound represented by Formula 1.

[0120] According to another embodiment, the hypervalent iodine-containing compound may be one of the following Compounds 1 to 10:

[0121]

[0122] Compound 1 is [hydroxy(toluenesulfonyloxy)iodo]benzene (HTIB), Compound 2 is [hydroxy(methanesulfonyloxy)iodo]benzene (HMIB), Compound 3 is (diacetoxyiodo)benzene (PIDA), Compound 4 is [bis(trifluoroacetoxy)iodo]benzene (PIFA), Compound 5 is [hydroxy(toluenesulfonyloxy)iodo](methyl)benzene (HTI(tolyl)), Compound 6 is [hydroxy(toluenesulfonyloxy)iodo]anisole (HTI(anisole)), Compound 7 is (5-trimethylammonio-1,3-dioxo-1,3-dihydro-1λ 5-benzod[d][1,2]iodoxol-1-olate anion) (AIBX), Compound 8 is 1-hydroxy-1,3-dioxo-1,3-dihydro-1λ 5 -benzod[d][1,2]iodoxole-4-carboxylic acid (mIBX), Compound 9 is 1-hydroxy-1,3-dioxo-1,3-dihydro-1λ 5 -benzod[d][1,2]iodoxole-5-potassium sulfonate (IBX-SO3K), and Compound 10 is potassium 4-iodoxybenzenesulfonate (PIBS).

[0123] The amount of the hypervalent iodine-containing compound may be about 0.005 wt% to about 1 wt%, about 0.005 wt% to about 0.5 wt%, about 0.005 wt% to about 0.1 wt%, about 0.005 wt% to about 0.05 wt%, or about 0.005 wt% to about 0.01 wt%, based on 100 wt% of the etching composition. When the amount of the hypervalent iodine-containing compound is within the above range, the etching selectivity can be further improved.

[0124] In the case where the etching composition includes the hypervalent iodine-containing compound, excellent etching selectivity for the metal-containing layer can be maintained (for example, the etching selectivity capable of selectively and mainly removing the titanium nitride-containing region among the titanium nitride-containing region and the molybdenum-containing region).

[0125] Furthermore, in the case where the etching composition includes the hypervalent iodine-containing compound, the etching rate deviation and the etching selectivity deviation can be reduced over the entire region of the metal-containing layer, and thus excellent etching uniformity can be obtained. By obtaining the etching uniformity as described above, insufficient etching occurring in some regions of the substrate in a large-area substrate can be restricted and / or prevented, and thus the precision of the etching process can be improved.

[0126] That is, in the case where the etching composition includes the hypervalent iodine-containing compound, "both" excellent etching selectivity and excellent etching uniformity can be obtained. Therefore, by using the etching composition, the efficiency, precision, and productivity of the etching process can be improved.

[0127] acid

[0128] The acid can be used to etch the metal-containing layer together with the hypervalent iodine-containing compound.

[0129] The acid may include a nitric acid-based inorganic acid, a sulfuric acid-based inorganic acid, a phosphoric acid-based inorganic acid, a chlorine-based inorganic acid, a fluorine-based inorganic acid, or any combination thereof.

[0130] According to one embodiment, the acid may include a fluorine-based inorganic acid.

[0131] For example, the fluorine-based inorganic acid may include hydrofluoric acid (HF), tetrafluoroboric acid, hexafluorosilicic acid, H2ZrF6, H2TiF6, HPF6, or any combination thereof.

[0132] The amount (by weight) of the acid may be, for example, from about 0.0001 wt% to about 20 wt%, from about 0.0001 wt% to about 10 wt%, from about 0.0001 wt% to about 5 wt%, from about 0.0001 wt% to about 1 wt%, from about 0.001 wt% to about 20 wt%, from about 0.001 wt% to about 10 wt%, from about 0.001 wt% to about 5 wt%, or from about 0.001 wt% to about 1 wt%, based on 100 wt% of the etching composition. When the amount of the acid satisfies the above range, the etching performance of the etching composition can be improved while maintaining the pH of the etching composition within an appropriate range.

[0133] According to another embodiment, the acid may be an organic acid, such as acetic acid, tartaric acid, and benzoic acid.

[0134] pH regulator

[0135] The pH regulator is used to maintain the pH of the etching composition within an appropriate range.

[0136] The pH regulator may be any known material suitable for use as a pH regulator in an etching composition.

[0137] According to one embodiment, the pH regulator may be selected from water-soluble substances and may include methanesulfonic acid (MSA), ethanesulfonic acid, phosphoric acid, sulfuric acid, hydrogen chloride, or any combination thereof.

[0138] The etching composition as described above may have a pH of from 0 to about 8.0, from 0 to about 7.0, from 0 to about 6.0, from 0 to about 5.0, from 0 to about 4.0, from 0 to about 3.0, from about 1.0 to about 8.0, from about 1.0 to about 7.0, from about 1.0 to about 6.0, from about 1.0 to about 5.0, from about 1.0 to about 4.0, from about 1.0 to about 3.0, from about 2.0 to about 8.0, from about 2.0 to about 7.0, from about 2.0 to about 6.0, from about 2.0 to about 5.0, from about 2.0 to about 4.0, or from about 2.0 to about 3.0.

[0139] For example, the etching composition may have a pH of from 0 to about 4.0, from 0 to about 3.5, from 0 to about 3.0, from 0 to about 2.0, from about 0.5 to about 4.0, from about 0.5 to about 3.5, from about 0.5 to about 3.0, or from about 0.5 to about 2.0. When the etching composition has a pH within the above ranges, the interaction between the metal atoms of the metal-containing layer and the iodine(III)-containing compound can occur more smoothly (steadily).

[0140] According to one embodiment, the etching composition can be used in an etching process and / or a CMP process for the metal-containing layer. The metal-containing layer is as described above.

[0141] Alternatively, the etching composition can be used as an etching by-product remover, a post-etching by-product remover, an ashing by-product remover, a cleaning composition, a photoresist (PR) remover, an etching composition for a packaging process, a cleaner for a packaging process, a wafer adhesive remover, an etchant, a post-etching residue stripper, an ash residue cleaner, a photoresist (PR) residue stripper, a CMP cleaner, or a post-CMP cleaner.

[0142] Method for etching a metal-containing layer and method for manufacturing a semiconductor device

[0143] The metal-containing layer can be effectively etched by using the etching composition as described above.

[0144] Referring to Figure 1 , the method for etching a metal-containing layer according to an embodiment may include: preparing a substrate S100 provided with a metal-containing layer; and performing an etching process on the metal-containing layer using the etching composition to remove at least a part of the metal-containing layer S110.

[0145] The metal-containing layer is as described above.

[0146] For example, the metal-containing layer may include indium (In), titanium (Ti), aluminum (Al), tungsten (W), lanthanum (La), scandium (Sc), gallium (Ga), zinc (Zn), hafnium (Hf), molybdenum (Mo), or any combination thereof.

[0147] As another example, the metal-containing layer may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.

[0148] By including the iodine - containing compound as described above, the etching composition can have excellent etching selectivity to the metal - containing layer and excellent etching uniformity over the entire area of the metal - containing layer “both”, thereby improving the efficiency, precision, and productivity of the etching process. Therefore, by using the etching process of the metal - containing layer employing the etching composition as described above, a semiconductor device having excellent performance can be manufactured.

[0149] Figure 2 and 3 are diagrams for schematically describing a method of etching a metal - containing layer according to an embodiment.

[0150] Referring Figure 2 , a substrate 100 provided with a metal - containing layer 120 is provided. An intermediate layer 110 may be disposed between the substrate 100 and the metal - containing layer 120. Although not shown in Figure 2 , circuit elements (e.g., transistor gates, metal wires, impurity regions, and semiconductor layers) may be located in the substrate 100, on the substrate 100, between the substrate 100 and the intermediate layer 110, etc. According to an embodiment, the metal - containing layer 120 may be directly located on the substrate 100, and the intermediate layer 110 may be omitted.

[0151] The metal - containing layer 120 may include a first region 121 and a second region 122. The etching rate of the composition for etching the second region 122 may be greater than the etching rate of the composition for etching the first region 121.

[0152] Referring Figure 3 , a pattern 125 of the metal - containing layer may be formed by separately etching at least a part of the first region 121 and at least a part of the second region 122 in the etching process of the metal - containing layer 120 by using the etching composition. The etching process may be performed by bringing at least a part of the first region 121 and at least a part of the second region 122 into contact with the etching composition.

[0153] The etching composition may separately etch at least a part of the first region 121 and at least a part of the second region 122. In Figure 3 , the pattern 125 of the metal - containing layer formed after etching may include some parts or more of the second region 122, but various modifications may be possible. If necessary, an etching process may be performed to completely remove the second region 122 from the pattern 125 of the metal - containing layer.

[0154] According to another embodiment, the first region 121 may include a metal oxide (e.g., alumina), silicon oxide, tungsten, or any combination thereof.

[0155] According to another embodiment, the second region 122 may include titanium nitride.

[0156] According to another embodiment, the second region 122 may include i) titanium nitride, ii) titanium nitride further including indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) any combination thereof.

[0157] According to another embodiment, each of the first region 121 and the second region 122 may include i) titanium nitride, ii) titanium nitride further including indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) any combination thereof.

[0158] According to another embodiment, the first region 121 may include molybdenum, and the second region 122 may not include molybdenum.

[0159] According to another embodiment, the first region 121 may include molybdenum, and the second region 122 may include titanium nitride (TiN).

[0160] According to another embodiment, the first region 121 may be a molybdenum (Mo) layer, and the second region 122 may be a titanium nitride (TiN) layer.

[0161] According to another embodiment, the etching rate ratio of the second region 122 to the first region 121 by the etching composition may be about 3 to about 30, about 3 to about 20, about 3 to about 15, or about 3 to about 10. The etching rate ratio of the second region 122 to the first region 121 can be obtained by dividing the second etching rate at which the composition etches the second region 122 by the first etching rate at which the composition etches the first region 121. In a case where the etching rate ratio of the second region 122 to the first region 121 by the etching composition satisfies the above range, the efficiency and productivity of the etching process can be improved.

[0162] According to another embodiment, the first region 121 may include molybdenum, the second region 122 may include titanium nitride, and the etching rate ratio of the second region 122 to the first region 121 by the etching composition (hereinafter, referred to as "R(TiN / Mo)") may be about 3 to about 30, about 3 to about 20, about 3 to about 15, or about 3 to about 10. R(TiN / Mo) can be obtained by dividing the etching rate at which the composition etches the second region 122 including titanium nitride by the etching rate at which the composition etches the first region 121 including molybdenum.

[0163] Referring to Figure 1 , a method of manufacturing a semiconductor device according to an embodiment may include: preparing a substrate S100 provided with a metal-containing layer; performing an etching process on the metal-containing layer by using the etching composition to remove at least a part of the metal-containing layer S110; and performing subsequent manufacturing processes S120 to manufacture a semiconductor device.

[0164] Hereinafter, one or more exemplary embodiments will be described in further detail with reference to the following examples and comparative examples. These examples and comparative examples are not intended to limit the scope of the inventive concept.

[0165] Examples 1 and 2 and Comparative Examples 1A, 1B, 2A, 2B, 3A, and 3B

[0166] 0.05 wt% of an acid, 0.6 wt% of a pH adjuster, and the oxidizing agents shown in Table 1 were each mixed in the amounts described therein to prepare the etching compositions of Examples 1 and 2 and Comparative Examples 1A, 1B, 2A, 2B, 3A, and 3B. The acid was hydrofluoric acid (HF), and the pH adjuster was methanesulfonic acid (MSA). The balance of each etching composition was water (deionized water).

[0167] Evaluation Example 1

[0168] After adding the etching composition of Example 1 to two beakers and heating to 70 °C, a titanium nitride layer (TiN layer) sample having a size of 1 cm x 1 cm and a molybdenum layer (Mo layer) sample having a size of 1 cm x 1 cm were respectively immersed in the etching composition in the beakers for 5 minutes. Then, the thicknesses of the titanium nitride layer and the molybdenum layer were measured by using an ellipsometer (M-2000, J.A. Woolam), a four-point probe, and X-ray fluorescence (XRF) to evaluate the etching rate of the TiN layer by the etching composition of Example 1 The etching rate of the Mo layer Subsequently, R(TiN / Mo) of the etching composition of Example 1 was evaluated by dividing the etching rate of the titanium nitride layer by the etching rate of the molybdenum layer, and the results are shown in Table 1.

[0169] This test was repeated using the etching compositions of Example 2 and Comparative Examples 1A, 1B, 2A, 2B, 3A, and 3B, and the results are shown in Table 1.

[0170] Table 1

[0171]

[0172]

[0173] Referring to Table 1, it was confirmed that the etching compositions of Comparative Examples 1B, 2B, 3A, and 3B had an R(TiN / Mo) ratio of not more than 1, indicating poor etching selectivity (the etching selectivity of selectively and mainly removing the titanium nitride layer among the TiN layer and the Mo layer).

[0174] Subsequently, Evaluation Example 2 was conducted to evaluate the etching uniformity of the etching compositions of Example 1 and Comparative Example 1A.

[0175] Evaluation Example 2

[0176] After adding the etching composition of Example 1 to three beakers and heating to 70 °C, i) a titanium nitride layer (TiN layer) sample with a size of 1 cm x 1 cm and a molybdenum layer (Mo layer) sample with a size of 1 cm x 1 cm were simultaneously immersed in the etching composition in the first beaker for 5 minutes, ii) a titanium nitride layer (TiN layer) sample with a size of 1 cm x 2 cm and a molybdenum layer (Mo layer) sample with a size of 1 cm x 2 cm were simultaneously immersed in the etching composition in the second beaker for 5 minutes, and iii) a titanium nitride layer (TiN layer) sample with a size of 2 cm x 2 cm and a molybdenum layer (Mo layer) sample with a size of 2 cm x 2 cm were simultaneously immersed in the etching composition in the third beaker for 5 minutes. Then, the thickness of the samples was measured using an ellipsometer (M-2000, J.A. Woolam), a four-point probe, and X-ray fluorescence (XRF) to evaluate the etching rate of the TiN layer by the etching composition of Example 1 and the etching rate of the Mo layer and the results are shown in Table 2

[0177] For comparison, the relative values (%) of the etching rate of the TiN layer with a size of 1 cm x 2 cm and the relative values (%) of the etching rate of the TiN layer with a size of 2 cm x 2 cm were calculated as values relative to the etching rate of the TiN layer with a size of 1 cm x 1 cm, and the relative values (%) of the etching rate of the Mo layer with a size of 1 cm x 2 cm and the relative values (%) of the etching rate of the Mo layer with a size of 2 cm x 2 cm were calculated as values relative to the etching rate of the Mo layer with a size of 1 cm x 1 cm. The results are shown in Table 2

[0178] Subsequently, R(TiN / Mo) of the sample with a size of 1 cm x 1 cm by the etching composition of Example 1, R(TiN / Mo) of the sample with a size of 1 cm x 2 cm by the etching composition of Example 1, and R(TiN / Mo) of the sample with a size of 2 cm x 2 cm by the etching composition of Example 1 were evaluated by dividing the etching rate of the TiN layer by the etching rate of the Mo layer for samples of the same size. The results are shown in Table 2

[0179] For comparison, the relative values (%) of R(TiN / Mo) of the 1 cm x 2 cm sample and the relative values (%) of R(TiN / Mo) of the 2 cm x 2 cm sample were calculated as values relative to R(TiN / Mo) (100%) of the 1 cm x 1 cm sample. The results are shown in Table 2

[0180] This test was repeated using the etchant composition of Comparative Example 1A, and the results are shown in Table 2.

[0181] Table 2

[0182]

[0183] Referring to Table 2, although the size of the sample increased, it was confirmed that with the etchant composition of Example 1, an etching rate of 88% or more was maintained in the case of the TiN layer, and an etching rate of 83% or more was maintained in the case of the Mo layer. However, in the case of the etchant composition of Comparative Example 1A, it was confirmed that as the sample size increased, the etching rates of the TiN layer and the Mo layer decreased to levels of "not more than 57%" and "not more than 41%", respectively.

[0184] Subsequently, based on Table 2, the average value and standard deviation of the relative values of R(TiN / Mo) for the three types of samples of the etchant compositions of Example 1 and Comparative Example 1A were calculated and are shown in Table 3.

[0185] Table 3

[0186]

[0187] Referring to Table 3, it was confirmed that for the three types of samples, the standard deviation of the relative value of R(TiN / Mo) of the etchant composition of Comparative Example 1A was about three times or more that of the relative value of R(TiN / Mo) of the etchant composition of Example 1. That is, it was confirmed that although the sample size increased, the change in R(TiN / Mo) of the etchant composition of Example 1 was smaller than that of the etchant composition of Comparative Example 1A, and thus it was confirmed that the etchant composition of Example 1 had excellent etching uniformity.

[0188] Since the etchant composition has both excellent etching selectivity and excellent etching uniformity with respect to the metal-containing layer as the layer to be etched, the efficiency, precision, and productivity of the etching process can be improved. Therefore, by using the etchant composition, an effective etching process and / or chemical mechanical polishing process can be performed on the layer to be etched. Therefore, a semiconductor device manufactured by etching a metal-containing layer using the etchant composition can have excellent performance.

[0189] It should be understood that the embodiments described herein are to be considered in a descriptive sense only and not for purposes of limitation. The description of a feature or aspect in each embodiment should typically be considered applicable to other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the accompanying drawings, those of ordinary skill in the art will understand that various changes in form and detail may be made therein without departing from the spirit and scope as defined by the appended claims.

Claims

1. An etching composition comprising: Compounds containing high-valent iodine.

2. The etching composition according to claim 1, further comprising: acid; and water.

3. The etching composition according to claim 1, The high-valent iodine-containing compound includes trivalent iodine (iodine (III)) or pentavalent iodine (iodine (V)).

4. The etching composition according to claim 1, wherein the high-valent iodine-containing compound comprises iodine and one or more carbon atoms, and One of the carbon atoms is chemically bonded to iodine.

5. The etching composition according to claim 1, wherein the hypervalent iodine-containing compound comprises iodine and n ligands bound to the iodine, and wherein at least one of the ligands comprises a C1-C 30 Aromatic cyclic groups.

6. The etching composition according to claim 1, The high-valent iodine-containing compound is a compound represented by the following formula 1, a compound represented by the following formula 2, a compound represented by the following formula 3, a compound represented by the following formula 4, or a combination thereof: <Formula 1> I(L1)(L2)(L3) <Formula 2> <Formula 3> <Formula 4> Wherein in Formulas 1 to 4, L1, L2, L3, and L4 are each independently a ligand that binds to iodine of one of Formulas 1 to 4, L1 and L2 are each independently *-OH, *-SH, *-O(Q1), *-S(Q1), *-OS(═O)2-Q1, *-OC(═O)-Q1, *-SC(═O)-Q1, *-OC(═S)-Q1, *-SC(═S)-Q1, *-S(═O)2-Q1, *-C(═O)-Q1, *-C(═S)-Q1, *-S(═O)2-O-Q1, *-C(═O)-O-Q1, or *-C(═S)-O-Q1, L3 and L4 are each independently unsubstituted or substituted with 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, *-SO3(Q 11 )、C1-C 30 Alkyl, C1-C 30 Alkoxy, C2-C 30 Alkenyl, C3-C 30 Carbocyclic groups, C1-C 30 Heterocyclic groups, or combinations thereof, Ring CY2 is C3-C 30 Carbocyclic group or C1-C 30 Heterocyclic groups, T + is [N(Q 21 )(Q 22 )(Q 23 )] + , Q1, Q2, Q 21 , Q 22 , and Q 23 Each independently is: Hydrogen, deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH2, *-C(=O)-NH(CH3), *-C(=O)-N(CH3)2, *-NH-C(=O)-NH2, *-NH-C(=O)-NH(CH3), *-NH-C(=O)-N(CH3)2, *-NH2, *-NH(CH3), *-N(CH3)2, or *-SO3(Q 11 );or C1-C 30 Alkyl, C1-C 30 Alkoxy, C2-C 30 Alkenyl, C3-C 30 Carbocyclic group, or C1-C 30 Heterocyclic groups: deuterium, *-F, *-Cl, *-Br, *-I, *-OH, *-SH, *-C(=O)-H, *-C(=O)-OH, *-C(=O)-NH2, *-C(=O)-NH(CH3), *-C(=O)-N(CH3)2, *-NH-C(=O)-NH2, *-NH-C(=O)-NH(CH3), *-NH-C(=O)-N(CH3)2, *-NH2, *-NH(CH3), *-N(CH3)2, *-SO3(Q 11 )、C1-C 30 Alkyl, C1-C 30 Alkoxy, C2-C 30 Alkenyl, C3-C 30 Carbocyclic groups, C1-C 30 Heterocyclic groups, or combinations thereof, n2 is an integer from 0 to 10, Q 11 is hydrogen or an alkali metal, and * is the binding site with the adjacent atom.

7. The etching composition according to claim 6, Among them, L2 is *-OS(=O)2-Q1, *-OC(=O)-Q1, *-SC(=O)-Q1, *-OC(=S)-Q1, *-SC(=S)-Q1, *-S( =O)2-Q1, *-C(=O)-Q1, *-C(=S)-Q1, *-S(=O)2-O-Q1, *-C(=O)-O-Q1, or *-C(=S)-O-Q1.

8. The etching composition according to claim 6, wherein Q1 is C1-C1 which is unsubstituted or substituted as follows 10 Alkyl, C1-C 10 Alkoxy, phenyl, naphthyl, or pyridyl: deuterium, *-F, C1-C 10 Alkyl, C1-C 10 Alkoxy, phenyl, naphthyl, pyridyl, or a combination thereof, L3 is phenyl, naphthyl, or pyridyl, each of which is unsubstituted or substituted by: deuterium, *-F, C1-C 10 Alkyl, C1-C 10 Alkoxy, phenyl, naphthyl, pyridyl, or a combination thereof, Q2 is hydrogen, *-C(=O)-OH, or *-SO3 (Q 11 ), L4 is phenyl, naphthyl, or pyridyl, each of which is unsubstituted or substituted by: deuterium, *-F, *-SO3 (Q 11 )、C1-C 10 Alkyl, C1-C 10 alkoxy, phenyl, naphthyl, pyridyl, or a combination thereof.

9. The etching composition according to claim 1, wherein The compound containing high-valent iodine is one of the following compounds 1 to 10:

10. The etching composition according to claim 1, The amount of the high-valent iodine-containing compound is 0.005 wt % to 1 wt %, based on 100 wt % of the etching composition.

11. The etching composition according to claim 2, The acid includes a fluorine-based inorganic acid.

12. The etching composition according to claim 2, The acid comprises hydrofluoric acid (HF), tetrafluoroboric acid, hexafluorosilicic acid, H2ZrF6, H2TiF6, HPF6, or a combination thereof.

13. The etching composition according to claim 2, The amount of the acid is 0.0001 wt % to 20 wt %, based on 100 wt % of the etching composition.

14. The etching composition according to claim 1, further comprising a pH adjuster.

15. The etching composition according to claim 1, The etching composition has a pH of 0 to 4.

0.

16. A method of etching a metal-containing layer, the method comprising: preparing a substrate provided with a metal-containing layer; as well as The metal-containing layer is subjected to an etching process using the etching composition according to any one of claims 1 to 15 to remove at least a portion of the metal-containing layer.

17. A method for manufacturing a semiconductor device, the method comprising: preparing a substrate provided with a metal-containing layer; performing an etching process on the metal-containing layer using the etching composition according to any one of claims 1 to 15 to remove at least a portion of the metal-containing layer; and Subsequent manufacturing processes are performed to manufacture semiconductor devices.

18. The method according to claim 16 or 17, The metal-containing layer includes indium (In), titanium (Ti), aluminum (Al), tungsten (W), lanthanum (La), scandium (Sc), gallium (Ga), zinc (Zn), hafnium (Hf), molybdenum (Mo), or a combination thereof.

19. The method according to claim 16 or 17, wherein the metal-containing layer comprises a first region and a second region, A second etch rate at which the composition etches the second region is greater than a first etch rate at which the etching composition etches the first region, and The etching process is performed by contacting at least a portion of the first region and at least a portion of the second region with the etching composition.

20. The method according to claim 19, wherein the first region comprises molybdenum, and The second region includes titanium nitride (TiN).

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