Etching composition, metal containing film etching method using the same, and manufacturing method for semiconductor element using the same

Abstract

To provide an etching composition, a metal containing film etching method using the same, and a manufacturing method for a semiconductor element using the same.SOLUTION: Provided are an etching composition including a hypervalent iodine containing compound, a metal containing film etching method using the same, and a manufacturing method for a semiconductor element using the same.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

[0002] In order to meet the excellent performance and low price required by consumers, an increase in the integration degree and an improvement in the reliability of semiconductor devices are required. As the integration degree of semiconductor devices increases, damage to the components of semiconductor devices in the manufacturing process of semiconductor devices will have a greater impact on the reliability and electrical characteristics of semiconductor memory devices. In particular, in the manufacturing process of semiconductor devices, various etching processes are performed on a predetermined film (for example, a metal-containing film). In order to effectively perform the etching process, there is a continuous need for an etching composition that can provide an excellent etching rate, excellent etching selectivity with respect to adjacent films, the absence of surface residues after etching, excellent storage stability, and the like.

Summary of the Invention

Problems to be Solved by the Invention

[0003] The problem to be solved by the present invention is to provide an etching composition that has excellent etching selectivity with respect to a metal-containing film that is a film to be etched, while increasing the productivity and efficiency of the etching process.

Means for Solving the Problems

[0004] According to one aspect, an etching composition containing a hypervalent iodine-containing compound is provided.

[0005] The etching composition may further contain an acid and water.

[0006] The hypervalent iodine-containing compound may contain trivalent iodine (iodine(III)) or pentavalent iodine (iodine(V)).

[0007] The hypervalent iodine-containing compound contains iodine and at least one carbon, and one of the carbons is bonded to the iodine by a chemical bond.

[0008] The hypervalent iodine-containing compound contains iodine and n ligands bonded to the iodine, and at least one of the n ligands may contain an aromatic ring group having 1 to 30 carbon atoms.

[0009] The content of the hypervalent iodine-containing compound may be 0.005 wt% to 1 wt% per 100 wt% of the etching composition.

[0010] The acid may contain a fluorine-based inorganic acid.

[0011] The content of the acid may be 0.0001 wt% to 20 wt% per 100 wt% of the etching composition.

[0012] The etching composition may further contain a pH adjuster. The etching composition can have a pH of 0 to 4.0.

[0013] According to another aspect, preparing a substrate provided with a metal-containing film; performing an etching process using the etching composition on the metal-containing film to remove at least a part of the metal-containing film, a metal-containing film etching method is provided.

[0014] The metal-containing film may contain indium (In), titanium (Ti), aluminum (Al), tungsten (W), lanthanum (La), scandium (Sc), gallium (Ga), zinc (Zn), hafnium (Hf), molybdenum (Mo), or any combination thereof.

[0015] The metal-containing film includes a first region and a second region, the second etching rate at which the etching composition etches the second region is faster than the first etching rate at which the etching composition etches the first region, the etching step is 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.

[0016] The first region contains molybdenum, and the second region contains titanium nitride (TiN).

[0017] According to yet another aspect, providing a substrate provided with a metal-containing film; performing an etching step using the etching composition on the metal-containing film to remove at least a portion of the metal-containing film; performing subsequent manufacturing process(es) to fabricate a semiconductor device, a method of manufacturing a semiconductor device is provided.

Advantages of the Invention

[0018] The etching composition simultaneously has excellent etching selectivity and etching uniformity with respect to the metal-containing film which is the film to be etched, and thus can increase the efficiency, accuracy, and productivity of the etching step. Therefore, by using the etching composition, an effective etching step and / or a chemical mechanical polishing (CMP) step can be performed on the film to be etched. Accordingly, a semiconductor device fabricated using the metal-containing film etching step using the etching composition can have excellent performance.

Brief Description of the Drawings

[0019]

Figure 1

Figure 2

Figure 3

Embodiments for Carrying Out the Invention

[0020] Etching target film The film to be etched includes a metal-containing film. Therefore, the etching composition can be used in an etching process and / or a CMP process of a metal-containing film.

[0021] The metals contained in the metal-containing film may include alkali metals (e.g., sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), etc.), alkaline earth metals (e.g., beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), etc.), lanthanide metals (e.g., lanthanum (La), europium (Eu), terbium (Tb), ytterbium (Yb), etc.), transition metals (e.g., scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), nickel (Ni), copper (Cu), silver (Ag), zinc (Zn), etc.), post-transition metals (e.g., aluminum (Al), gallium (Ga), indium (In), thallium (Tl), tin (Sn), bismuth (Bi), etc.), or any combination thereof.

[0022] According to one embodiment, the metal-containing film contains 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.

[0023] According to other embodiments, the metal-containing film contains indium (In), titanium (Ti), aluminum (Al), tungsten (W), lanthanum (La), scandium (Sc), gallium (Ga), zinc (Zn), hafnium (Hf), molybdenum (Mo), or any combination thereof.

[0024] For example, the metal-containing film contains aluminum, titanium, lanthanum, tungsten, molybdenum, or any combination thereof.

[0025] As yet another example, the metal-containing film contains titanium. As yet another example, the metal-containing film contains titanium and aluminum.

[0026] As yet another example, the metal-containing film contains tungsten. As yet another example, the metal-containing film contains molybdenum.

[0027] The metal-containing film may contain a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.

[0028] The metal-containing film contains a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof, and the metals contained in each of the metal, the metal nitride, the metal oxide, and the metal oxynitride include indium (In), titanium (Ti), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), zinc (Zn), hafnium (Hf), or any combination thereof.

[0029] The metal-containing film contains a metal nitride. The metal contained in the metal nitride includes indium, titanium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof.

[0030] As yet another example, the metal-containing film contains titanium nitride. The titanium nitride may further contain indium, aluminum, lanthanum, scandium, gallium, hafnium, zinc, or any combination thereof. As yet another example, the metal-containing film includes titanium nitride (TiN), titanium nitride further containing aluminum (for example, titanium / aluminum nitride or TiAlN), titanium nitride further containing lanthanum, and the like.

[0031] As yet another example, the metal-containing film contains a metal oxide. The metal contained in the metal oxide includes titanium, aluminum, lanthanum, scandium, gallium, hafnium, or any combination thereof. For example, the metal-containing film includes aluminum oxide (for example, Al2O3), IGZO (indium gallium zinc oxide), and the like.

[0032] As yet another example, the metal-containing film contains the metal and a metal nitride. As yet another example, in addition to the metal, the metal-containing film may further contain a metalloid (for example, boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), etc.), a non-metal (for example, nitrogen (N), phosphorus (P), oxygen (O), sulfur (S), selenium (Se), etc.), and any combination thereof.

[0033] For example, the metal-containing film may further contain silicon oxide. The metal-containing film may have a single-layer structure containing one or more substances (or consisting of), or may have a multilayer structure or a pattern structure containing different substances from each other.

[0034] For example, the metal-containing film can have: i) a single-layer structure containing (or consisting of) titanium nitride; ii) a bilayer structure or pattern structure including a first layer containing (or consisting of) titanium nitride and a second layer containing (or consisting of) titanium nitride further containing aluminum; iii) a bilayer structure or pattern structure including a first layer containing (or consisting of) titanium nitride and a second layer containing (or consisting of) aluminum oxide; or iv) a bilayer structure or pattern structure including a first layer containing (or consisting of) titanium nitride and a second layer containing (or consisting of) molybdenum, etc.

[0035] According to still another embodiment, the metal-containing film includes a first region and a second region, and a second etching rate at which the etching composition etches the second region is faster than a first etching rate at which the etching composition etches the first region. During the etching process and / or polishing process on the metal-containing film, at least a part of the first region and at least a part of the second region are brought into contact with the etching composition. Since the second etching rate is faster than the first etching rate, the second region is etched faster than the first region.

[0036] For example, the first region may include a metal, a metal oxide (e.g., aluminum oxide), a silicon oxide, or any combination thereof.

[0037] According to one embodiment, the first region contains molybdenum. As another example, the second region may contain a metal nitride.

[0038] As still another example, the second region contains: i) titanium nitride; ii) titanium nitride further containing indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof; or iii) a combination thereof.

[0039] As yet another example, each of the first region and the second region includes i) titanium nitride, ii) titanium nitride further including indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination of them.

[0040] As yet another example, the first region includes aluminum and the second region does not include aluminum.

[0041] As yet another example, the first region includes titanium nitride further including aluminum (e.g., titanium / aluminum nitride or TiAlN), and the second region includes titanium nitride (TiN).

[0042] As yet another example, the first region includes a titanium nitride film further including aluminum (e.g., a titanium / aluminum nitride film or TiAlN film), and the second region includes a titanium nitride film (TiN film).

[0043] As yet another example, the first region is a titanium nitride film further including aluminum (e.g., a titanium / aluminum nitride film or TiAlN film), and the second region is a titanium nitride film (TiN film).

[0044] As yet another example, the first region includes molybdenum and the second region does not include molybdenum.

[0045] As yet another example, the first region includes molybdenum and the second region includes titanium nitride (TiN).

[0046] As yet another example, the first region includes a molybdenum film (Mo film) and the second region includes a titanium nitride film (TiN film).

[0047] As yet another example, the first region is a molybdenum film (Mo film) and the second region is a titanium nitride film (TiN film).

[0048] In this specification, when any film is etched, it means that at least a part of the substance constituting the film is removed.

[0049] Etching composition The etching composition contains a hypervalent iodine-containing compound.

[0050] In addition to the hypervalent iodine-containing compound, the etching composition may further contain an acid, a pH adjuster, a selective etching inhibitor, a selective etching accelerator, a solvent, water, or any combination thereof.

[0051] For example, in addition to the hypervalent iodine-containing compound, the etching composition further contains an acid and water. When the etching composition further contains an acid and water in addition to the hypervalent iodine-containing compound, the hypervalent iodine-containing compound can serve as an oxidizing agent.

[0052] As still another example, in addition to the hypervalent iodine-containing compound, the etching composition further contains a pH adjuster.

[0053] As still another example, in addition to the hypervalent iodine-containing compound, the etching composition further contains an acid, a pH adjuster, and water.

[0054] The etching composition can be used in the etching process and / or the CMP process of the etching target film described in this specification, for example, a metal-containing film.

[0055] Hypervalent iodine-containing compound The hypervalent iodine-containing compound can serve to etch the metal-containing film. For example, the hypervalent iodine-containing compound can serve to remove titanium atoms from the metal-containing film. As still another example, the hypervalent iodine-containing compound can serve as an oxidizing agent.

[0056] According to one embodiment, the hypervalent iodine-containing compound contains trivalent iodine (iodine(III)) or pentavalent iodine (iodine(V)).

[0057] According to another embodiment, the hypervalent iodine-containing compound contains iodine and at least one carbon, and one of the carbons is bonded to the iodine by a chemical bond.

[0058] According to still another embodiment, the hypervalent iodine-containing compound contains iodine and n ligands bonded to the iodine, where n is 1, 2, 3, 4, 5, or 6 (for example, 1, 2, or 3).

[0059] According to still another embodiment, at least one of the n ligands is an organic ligand. For example, at least one of the n ligands contains an aromatic ring group having 1 to 30 carbon atoms (for example, a benzene group, a naphthalene group, a pyridine group, a pyrimidine group, etc.).

[0060] According to still another embodiment, each of the n ligands is a monodentate ligand or a bidentate ligand.

[0061] According to still another embodiment, the hypervalent iodine-containing compound is a compound represented by the following Chemical Formula 1, a compound represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 3, a compound represented by the following Chemical Formula 4, or any combination thereof:

[0062] [Chemical Formula 1] I(L1)(L2)(L3)

[0063]

Chem.

[0064]

Chem.

[0065]

Chem.

[0066] In the above chemical formulas 1 to 4, L1, L2, L3 and L4 are each a ligand bonded to iodine in chemical formulas 1 to 4, L1 and L2 are, independently of each other, *-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, L3 and L4 are, independently of each other, 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 group, C1-C 30 alkoxy group, C2-C 30 alkenyl group, C3-C 30 carbocyclic group, C1-C 30 heterocyclic group, or a C3-C substituted or unsubstituted with any combination thereof 30 carbocyclic group or C1-C 30 heterocyclic group, Ring CY2 is a C3-C 30 carbocyclic group or C1-C 30 heterocyclic group, Q1 and Q2 are, independently 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), *-N(CH3)2, or *-SO3(Q 11 ); 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, *-SO3(Q 11 ), C1-C 30 alkyl group, C1-C 30 alkoxy group, C2-C 30 alkenyl group, C3-C 30 carbocyclic group, C1-C 30 heterocyclic group, or a substituted or unsubstituted C1-C 30 alkyl group, C1-C 30 alkoxy group, C2-C 30 alkenyl group, C3-C 30 carbocyclic group, or C1-C 30 heterocyclic group; and n2 is an integer from 0 to 10, Q 11 is hydrogen or an alkali metal, T + is [N(Q 21 )(Q 22 )(Q 23 )] + and the descriptions related to each of Q 21 ~Q 23 are the same as the description related to Q1, * is the bonding site with an adjacent atom.

[0067] For example, in the chemical formula 1, L2 is *-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.

[0068] According to one embodiment, in the chemical formulas 1 and 3, L1 is *-OH, *-O-S(=O)2-Q1, or *-O-C(=O)-Q1, and L2 is *-O-S(=O)2-Q1 or *-O-C(=O)-Q1.

[0069] According to another embodiment, in the chemical formula 1, L1 and L2 are identical to each other.

[0070] According to still another embodiment, in the chemical formula 1, L1 and L2 are different from each other.

[0071] According to still another embodiment, in the chemical formula 1, the bond between iodine and ligand L3 is an iodine-carbon bond.

[0072] According to still another embodiment, Q1 is deuterium, *-F, C1-C 10 alkyl group, C1-C 10 alkoxy group, phenyl group, naphthyl group, pyridinyl group, or a C1-C 10 alkyl group, C1-C 10 alkoxy group, phenyl group, naphthyl group, or pyridinyl group which is substituted or unsubstituted with any combination thereof.

[0073] According to still another embodiment, in the chemical formula 1, L3 is deuterium, *-F, C1-C 10 alkyl group, C1-C 10 alkoxy group, phenyl group, naphthyl group, pyridinyl group, or a phenyl group, naphthyl group, or pyridinyl group which is substituted or unsubstituted with any combination thereof.

[0074] According to still other embodiments, in Chemical Formulas 2 and 3, ring CY2 is a benzene group, a naphthalene group, a phenanthrene group, a pyridine group, a pyrimidine group, a pyrazine group, or a pyridazine group.

[0075] According to still other embodiments, in Chemical Formulas 2 and 3, Q2 is hydrogen, *-C(=O)-OH, or *-SO3(Q 11 ).

[0076] According to still other embodiments, in Chemical Formulas 2 and 3, n2 is 0, 1, or 2.

[0077] According to still other embodiments, in Chemical Formula 4, L4 is deuterium, *-F, *-SO3(Q 11 ), C1-C 10 alkyl group, C1-C 10 alkoxy group, phenyl group, naphthyl group, pyridinyl group, or a phenyl group, naphthyl group, or pyridinyl group which is substituted or unsubstituted with any combination thereof.

[0078] According to still other embodiments, the Q 11 is hydrogen, Li, Na, K, Rb, or Cs.

[0079] According to still other embodiments, in Chemical Formula 2, T + is [N(Q 21 )(Q 22 )(Q 23 )] + and Q 21 ~Q 23 are, independently of each other, deuterium, *-F, C1-C 10 alkyl group, C1-C 10 alkoxy group, or a C1-C 10 alkyl group, C1-C 10 alkoxy group, phenyl group, naphthyl group, or pyridinyl group which is substituted or unsubstituted with any combination thereof.

[0080] According to still other embodiments, the compound represented by Chemical Formula 2 is a compound represented by the following Chemical Formula 2A, and the compound represented by Chemical Formula 3 is a compound represented by the following Chemical Formula 3A:

[0081] [Chem.]

[0082] [Chem.]

[0083] In Chemical Formulas 2A and 3A, for L1, Q2, and T + refer to the descriptions given herein, n2 in Chemical Formula 2A is an integer from 0 to 3, and n2 in Chemical Formula 3A is an integer from 0 to 4.

[0084] According to still other embodiments, the hypervalent iodine-containing compound includes the compound represented by Chemical Formula 1.

[0085] According to still other embodiments, the hypervalent iodine-containing compound is one of the following Compounds 1 to 10.

[0086] [Chem.]

[0087] Compound 1 is [hydroxy(tosyloxy)iodo]benzene (HTIB), Compound 2 is [hydroxy(mesyloxy)iodo]benzene (HMIB), Compound 3 is (diacetoxyiodo)benzene (PIDA), Compound 4 is [bis(trifluoroacetoxy)iodo]benzene (PIFA), Compound 5 is [hydroxy(tosyloxy)iodo](methyl)benzene (HTI(tolyl)), Compound 6 is [hydroxy(tosyloxy)iodo]anisole (HTI(anisole)), Compound 7 is (5-trimethylammonio-1,3-dioxo-1,3-dihydro-1λ5 -benzod[d][1,2]iodoxol-1-olate anion)(AIBX), and compound 8 is 1-hydroxy-1,3-dioxo-1,3-dihydro-1λ 5 -benzod[d][1,2]iodoxole-4-carboxylic acid (mIBX), and compound 9 is potassium 1-hydroxy-1,3-dioxo-1,3-dihydro-1λ 5 -benzod[d][1,2]iodoxole-3-sulfonate (IBX-SO3K), and compound 10 is potassium 4-iodobenzenesulfonate (PIBS).

[0088] The content of the hypervalent iodine-containing compound is 0.005 wt% to 1 wt%, 0.005 wt% to 0.5 wt%, 0.005 wt% to 0.1 wt%, 0.005 wt% to 0.05 wt%, or 0.005 wt% to 0.01 wt% per 100 wt% of the etching composition. When the content of the hypervalent iodine-containing compound satisfies the above range, the etching selectivity can be further improved.

[0089] Since the etching composition contains a hypervalent iodine-containing compound, an excellent etching selectivity (for example, an etching selectivity in which the region containing titanium nitride can be selectively and predominantly removed among the region containing titanium nitride and the region containing molybdenum) for the metal-containing film can be maintained.

[0090] In addition, since the etching composition contains a hypervalent iodine-containing compound, the etching rate deviation and the etching selectivity deviation with respect to the total area of the metal-containing film are reduced, so that excellent etching uniformity can be ensured. By ensuring such etching uniformity, when the substrate including the metal-containing film has a large area, the phenomenon that the etching in a partial region of the substrate is insufficient is prevented, and the accuracy of the etching process can be improved.

[0091] That is, by including a hypervalent iodine-containing compound in the etching composition, excellent etching selectivity and excellent etching uniformity can be "simultaneously" ensured. Therefore, by using the etching composition, the efficiency, accuracy, and productivity of the etching process can be improved.

[0092] Acid The acid can, together with the hypervalent iodine-containing compound, play a role in etching a metal-containing film.

[0093] 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.

[0094] According to one embodiment, the acid includes a fluorine-based inorganic acid.

[0095] For example, the fluorine-based inorganic acid may include hydrofluoric acid (HF), tetrafluoroboric acid, hexafluorosilicic acid, H2ZrF6, H2TiF6, HPF6, or any combination thereof.

[0096] The content (by weight) of the acid is, for example, 0.0001 wt% to 20 wt%, 0.0001 wt% to 10 wt%, 0.0001 wt% to 5 wt%, 0.0001 wt% to 1 wt%, 0.001 wt% to 20 wt%, 0.001 wt% to 10 wt%, 0.001 wt% to 5 wt%, or 0.001 wt% to 1 wt% per 100 wt% of the etching composition. When the content of the acid satisfies the above-mentioned range, the etching performance of the etching composition is improved, and the pH of the etching composition can be maintained within an appropriate range.

[0097] According to still another example, the acid may be an organic acid, such as acetic acid, tartaric acid, benzoic acid, etc.

[0098] pH adjuster The pH adjuster plays a role in maintaining the pH of the etching composition within an appropriate range. As the pH adjuster, any known substance can be used.

[0099] According to one embodiment, the pH adjuster is selected from water-soluble substances and may include methanesulfonic acid (MSA), ethanesulfonic acid, phosphoric acid, sulfuric acid, hydrogen chloride, or any combination thereof.

[0100] The etching composition as described above can have a pH of 0 to 8.0, 0 to 7.0, 0 to 6.0, 0 to 5.0, 0 to 4.0, 0 to 3.0, 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, or 2.0 to 3.0.

[0101] For example, the etching composition can have a pH of 0 to 4.0, 0 to 3.5, 0 to 3.0, 0 to 2.0, 0.5 to 4.0, 0.5 to 3.5, 0.5 to 3.0, or 0.5 to 2.0. When the etching composition has a pH within the above range, the interaction between the metal atoms of the metal-containing film and the hypervalent iodine-containing compound occurs more smoothly.

[0102] According to one embodiment, the etching composition can be used in the metal-containing film etching process and / or the CMP process. Refer to the description of the metal-containing film in this specification for details.

[0103] Alternatively, the etching 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 substance remover, an etchant, a post-etch residue stripper, an ash residue cleaner, a photoresist (PR) residue stripper, a chemical mechanical polishing (CMP) cleaner, or a post-CMP cleaner, etc.

[0104] Method for etching metal-containing film and method for manufacturing semiconductor device The metal-containing film can be effectively etched using the etching composition as described above.

[0105] Referring to FIG. 1, one embodiment of the method for etching a metal-containing film includes a step S100 of preparing a substrate provided with a metal-containing film, and a step S110 of performing an etching process on the metal-containing film using the etching composition as described herein to remove at least a part of the metal-containing film.

[0106] For the description of the metal-containing film, refer to what is described herein. For example, the metal-containing film may include indium (In), titanium (Ti), aluminum (Al), tungsten (W), lanthanum (La), scandium (Sc), gallium (Ga), zinc (Zn), hafnium (Hf), molybdenum (Mo), or any combination thereof.

[0107] As yet another example, the metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or a combination thereof.

[0108] Since the etching composition contains a hypervalent iodine-containing compound as described above, it has excellent etching selectivity with respect to the metal-containing film and can have excellent etching uniformity with respect to the entire area of the metal-containing film "simultaneously", whereby the efficiency, accuracy, and productivity of the etching process can be increased. Therefore, by using the metal-containing film etching process using the etching composition as described above, a semiconductor device with excellent performance can be manufactured.

[0109] Figures 2 and 3 are drawings briefly explaining an embodiment of a method for etching a metal-containing film.

[0110] Referring to Figure 2, a substrate 100 provided with a metal-containing film 120 is provided. An intermediate layer 110 is disposed between the substrate 100 and the metal-containing film 120. Although not shown in Figure 2, circuitry elements (e.g., transistor gates, metal lines, impurity regions, semiconductor layers) can be disposed inside the substrate 100, on top of the substrate 100, and / or between the substrate 100 and the intermediate layer 110. According to one embodiment, the metal-containing film 120 is disposed directly on the substrate 100 and the intermediate layer 110 can be omitted.

[0111] The metal-containing film 120 includes a first region 121 and a second region 122. The second etching rate at which the etching composition etches the second region 122 is faster than the first etching rate at which the etching composition etches the first region 121.

[0112] Referring to FIG. 3, the etching composition can be used to etch the metal-containing film 120 to etch at least a part of the first region 121 and at least a part of the second region 122, respectively, to form a metal-containing film pattern 125. The etching process is 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.

[0113] The etching composition can etch at least a part of the first region 121 and at least a part of the second region 122, respectively. In FIG. 3, the metal-containing film pattern 125 formed after etching includes at least a part of the second region 122. However, when necessary, various modifications are possible, such as the etching process being performed so that the second region 122 is completely removed from the metal-containing film pattern 125.

[0114] According to another embodiment, the first region 121 includes a metal oxide (e.g., aluminum oxide), silicon oxide, tungsten, or any combination thereof.

[0115] According to still another embodiment, the second region 122 includes titanium nitride.

[0116] According to still another embodiment, the second region 122 includes i) titanium nitride, ii) titanium nitride further including indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof.

[0117] According to still another embodiment, each of the first region 121 and the second region 122 includes i) titanium nitride, ii) titanium nitride further including indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof.

[0118] According to still other embodiments, the first region 121 contains molybdenum, and the second region 122 does not contain molybdenum.

[0119] According to still other embodiments, the first region 121 contains molybdenum, and the second region 122 contains titanium nitride (TiN).

[0120] According to still other embodiments, the first region 121 is a molybdenum film (Mo), and the second region 122 is a titanium nitride film (TiN film).

[0121] According to still other embodiments, the etching rate ratio of the second region 122 to the first region 121 of the etching composition is 3 to 30, 3 to 20, 3 to 15, or 3 to 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 etching composition etches the second region 122 by the first etching rate at which the etching composition etches the first region 121. When the etching rate ratio of the second region 122 to the first region 121 of the etching composition satisfies the above range, the efficiency and productivity of the etching process can be improved.

[0122] According to still other embodiments, the first region 121 contains molybdenum, the second region 122 contains titanium nitride, and the etching rate ratio of the second region 122 to the first region 121 of the etching composition (hereinafter referred to as "R(TiN / Mo)") is 3 to 30, 3 to 20, 3 to 15, or 3 to 10. The R(TiN / Mo) can be obtained by dividing the rate at which the etching composition etches the second region 122 containing titanium nitride by the rate at which the etching composition etches the first region 121 containing molybdenum.

[0123] Referring to FIG. 1, a method for manufacturing a semiconductor device according to an embodiment includes a step S100 of preparing a substrate provided with a metal-containing film, a step S110 of performing an etching process using the etching composition on the metal-containing film to remove at least a part of the metal-containing film, and a step S120 of performing subsequent processes to fabricate a semiconductor device.

[0124] Examples 1 and 2, and Comparative Examples 1A, 1B, 2A, 2B, 3A and 3B An acid of 0.05 wt%, a pH adjuster of 0.6 wt%, an oxidizing agent with the contents and substances described in Table 1 were mixed to produce the etching compositions of Example 1 and 2, and Comparative Examples 1A, 1B, 2A, 2B, 3A, and 3B. Hydrofluoric acid (HF) was used as the acid, and methylsulfonic acid (MSA) was used as the pH adjuster. The remainder of each etching composition is water (deionized water).

[0125] Evaluation Example 1 The etching composition of Example 1 was placed in two beakers and heated to 70°C. Then, a titanium nitride film (TiN film) specimen with a size of 1 cm × 1 cm and a molybdenum film (Mo film) specimen with a size of 1 cm × 1 cm were immersed in each beaker for 5 minutes. After that, the thicknesses of the titanium nitride film and the molybdenum film were measured using an ellipsometer (M-2000, J.A. Woolam), a four-probe probe, and XRF (X-ray fluorescence). The etching rate (Å / min) of the etching composition of Example 1 for the titanium nitride film and the etching rate (Å / min) for the molybdenum film were evaluated. Then, the etching rate for the titanium nitride film was divided by the etching rate for the molybdenum film to evaluate R(TiN / Mo) of the etching composition of Example 1, and the results are shown in Table 1.

[0126] The above tests were repeated using the etching compositions of Example 2, Comparative Examples 1A, 1B, 2A, 2B, 3A, and 3B, and the results are shown in Table 1.

[0127]

Table 1

[0128]

Chem.

[0129] According to Table 1, since the etching compositions of Comparative Examples 1B, 2B, 3A, and 3B have an R(TiN / Mo) value of 1 or less, it can be confirmed that they have a poor etching selectivity (the etching selectivity for selectively and preferentially removing the titanium nitride film out of the titanium nitride film and the molybdenum film).

[0130] Next, the following Evaluation Example 2 was carried out to evaluate the etching uniformity of the etching compositions of Example 1 and Comparative Example 1A.

[0131] Evaluation Example 2 The etching composition of Example 1 was placed in three beakers and heated to 70 °C. Then, i) a titanium nitride film (TiN film) specimen with a size of 1 cm × 1 cm and a molybdenum film (Mo film) specimen with a size of 1 cm × 1 cm were simultaneously immersed in the first beaker for 5 minutes, ii) a titanium nitride film (TiN film) specimen with a size of 1 cm × 2 cm and a molybdenum film (Mo film) specimen with a size of 1 cm × 2 cm were simultaneously immersed in the second beaker for 5 minutes, and iii) a titanium nitride film (TiN film) specimen with a size of 2 cm × 2 cm and a molybdenum film (Mo film) specimen with a size of 2 cm × 2 cm were simultaneously immersed in the third beaker for 5 minutes. After that, the thickness of each specimen was measured using an ellipsometer (M-2000, J.A.Woolam), a four-probe probe, and XRF, and the etching rate (Å / min) of the etching composition of Example 1 for the titanium nitride film or the etching rate (Å / min) for the molybdenum film was evaluated, and the results are shown in Table 2. For comparison, the relative value (%) of the etching rate for the 1 cm × 2 cm size titanium nitride film and the relative value (%) of the etching rate for the 2 cm × 2 cm size titanium nitride film were converted as relative values with respect to the etching rate (100%) for the 1 cm × 1 cm size titanium nitride film, and the relative value (%) of the etching rate for the 1 cm × 2 cm size molybdenum film and the relative value (%) of the etching rate for the 2 cm × 2 cm size molybdenum film were converted as relative values with respect to the etching rate (100%) for the 1 cm × 1 cm size molybdenum film, and are shown in Table 2. Next, for specimens of the same size, the etching rate for the titanium nitride film was divided by the etching rate for the molybdenum film to evaluate R(TiN / Mo) for the 1 cm × 1 cm specimen of the etching composition of Example 1, R(TiN / Mo) for the 1 cm × 2 cm specimen of the etching composition of Example 1, and R(TiN / Mo) for the 2 cm × 2 cm specimen of the etching composition of Example 1, and the results are shown in Table 2. For comparison, the relative value (%) of R(TiN / Mo) for the 1 cm × 2 cm specimen and the relative value (%) of R(TiN / Mo) for the 2 cm × 2 cm specimen were converted as relative values with respect to R(TiN / Mo) (100%) for the 1 cm × 1 cm specimen, and are shown in Table 2.

[0132] The above tests were repeated using the etching compositions of Comparative Example 1A respectively, and the results are shown in Table 2.

[0133] [Table 2]

[0134] According to Table 2, it can be confirmed that the etching composition of Example 1 maintained an etching rate of 88% or more for the TiN film and an etching rate of 83% or more for the Mo film even when the specimen size increased. However, it can be confirmed that for the etching composition of Comparative Example 1A, as the specimen size increased, the etching rate of the TiN film and the etching rate of the Mo film decreased to levels of "57% or less" and "41% or less" respectively.

[0135] Next, based on Table 2, the average and standard deviation of the R(TiN / Mo) relative values of the etching composition of Example 1 and the etching composition of Comparative Example 1A for the three types of specimens were calculated and shown in Table 3.

[0136] [Table 3]

[0137] According to Table 3, it can be confirmed that the standard deviation of the R(TiN / Mo) relative value of the etching composition of Comparative Example 1A for the three types of specimens is about three times or more the standard deviation of the R(TiN / Mo) relative value of the etching composition of Example 1 for the three types of specimens. That is, it can be confirmed that the etching composition of Example 1 has a smaller change in R(TiN / Mo) even when the specimen size increases compared to the etching composition of Comparative Example 1A, and it can be confirmed that the etching composition of Example 1 has excellent etching uniformity. [Explanation of Signs]

[0138] 100 Substrate 110 Intermediate layer 120 Metal-containing film 121 First region 122 Second region 125 Metal-containing film pattern

Claims

1. An etching composition comprising a hypervalent iodine-containing compound.

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

3. The etching composition according to claim 1, wherein the hypervalent iodine-containing compound contains iodine(III) or iodine(V).

4. The etching composition according to claim 1, wherein the hypervalent iodine-containing compound contains iodine and at least one carbon, and one of the carbons is bonded to the iodine by a chemical bond.

5. The etching composition according to claim 1, wherein the hypervalent iodine-containing compound contains iodine and n ligands bonded to the iodine, and at least one of the n ligands contains an aromatic ring group having 1 to 30 carbon atoms.

6. The etching composition according to claim 1, wherein the hypervalent iodine-containing compound is a compound represented by the following Chemical Formula 1, a compound represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 3, a compound represented by the following Chemical Formula 4, or any combination thereof: [Chemical Formula 1] I (L １ )(L ２ )(L ３ ) 【Chemical 1】 【Chemical 2】 【Chemical Formula 3】 In Chemical Formulas 1 to 4 above, L １ 、 L ２ 、 L ３ and L ４ each is a ligand bonded to iodine of Chemical Formulas 1 to 4, L １ and L ２ are, independently of each other, *-OH, *-SH, *-O(Q １ ), *-S(Q １ ), *-O-S(=O) ２ -Q １ , *-O-C(=O)-Q １ , *-S-C(=O)-Q １ , *-O-C(=S)-Q １ , *-S-C(=S)-Q １ , *-S(=O) ２ -Q １ , *-C(=O)-Q １ , *-C(=S)-Q １ , *-S(=O) ２ -O-Q １ , *-C(=O)-O-Q １ , or *-C(=S)-O-Q １ wherein L ３ and L ４ are, independently of each other, 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 , *-SO ３ (Q １１ ), 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 heterocyclic group, or a C ３ -C ３０ carbocyclic group or C １ -C ３０ heterocyclic group which is substituted or unsubstituted with any combination thereof, and Ring CY ２ is C ３ -C ３０ a carbocyclic group or C １ -C ３０ a heterocyclic group, Q １ and Q ２ are, independently of one another, 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 ), *-N(CH ３ ); ２ , or *-SO ３ (Q １１ ); 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 , *-SO ３ (Q １１ ), 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 heterocyclic group, or a C １ -C ３０ alkyl group, C １ -C ３０ alkoxy group, C ２ -C ３０ alkenyl group, C ３ -C ３０ carbocyclic group, or a C １ -C ３０ heterocyclic group; wherein, n2 is an integer from 0 to 10, Q １１ is hydrogen or an alkali metal, T ＋ is [N(Q ２１ )(Q ２２ )(Q ２３ ) ＋ and the descriptions related to each of Q ２１ to Q ２３ are the same as the description related to Q １ ​ * is a bonding site with an adjacent atom.

7. L ２ is *-O-S(=O) ２ -Q １ 、*-O-C(=O)-Q １ 、*-S-C(=O)-Q １ 、*-O-C(=S)-Q １ 、*-S-C(=S)-Q １ 、*-S(=O) ２ -Q １ 、*-C(=O)-Q １ 、*-C(=S)-Q １ 、*-S(=O) ２ -O-Q １ 、*-C(=O)-O-Q １ 、or *-C(=S)-O-Q １ The etching composition according to claim 6, wherein it is as described above.

8. Q １ is deuterium, *-F, C １ -C １０ alkyl group, C １ -C １０ alkoxy group, phenyl group, naphthyl group, pyridinyl group, or a C which is substituted or unsubstituted with any combination thereof １ -C １０ alkyl group, C １ -C １０ alkoxy group, phenyl group, naphthyl group, or pyridinyl group, and L ３ is a phenyl group, naphthyl group, or pyridinyl group which is substituted or unsubstituted with deuterium, *-F, C １ -C １０ alkyl group, C １ -C １０ alkoxy group, phenyl group, naphthyl group, pyridinyl group, or any combination thereof, or a phenyl group, naphthyl group, or pyridinyl group which is unsubstituted or substituted with any combination thereof Q ２ is hydrogen, *-C(=O)-OH, or *-SO ３ (Q １１ ) and L ４ is deuterium, *-F, *-SO ３ (Q １１ )、C １ -C １０ an alkyl group, C １ -C １０ an alkoxy group, a phenyl group, a naphthyl group, a pyridinyl group, or a phenyl group, a naphthyl group, or a pyridinyl group substituted or unsubstituted with any combination thereof, the etching composition according to claim 6.

9. The etching composition according to claim 1, wherein the hypervalent iodine-containing compound is one of the following Compounds 1 to 10. 【Chemical 4】

10. The etching composition according to claim 1, wherein the content of the hypervalent iodine-containing compound is 0.005 wt% to 1 wt% per 100 wt% of the etching composition.

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

12. The acid is hydrofluoric acid, tetrafluoroboric acid, hexafluorosilicic acid, H ２ ZrF ６ 、H ２ TiF ６ 、HPF ６ 、 or any combination thereof, the etching composition according to claim 2.

13. The etching composition according to claim 2, wherein the content of the acid is 0.0001 wt% to 20 wt% per 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, having a pH of 0 to 4.

0.

16. Preparing a substrate provided with a metal-containing film; Performing an etching step using the etching composition according to any one of claims 1 to 15 on the metal-containing film to remove at least a part of the metal-containing film; A method for etching a metal-containing film, comprising:

17. The method for etching a metal-containing film according to claim 16, wherein the metal-containing film contains indium (In), titanium (Ti), aluminum (Al), tungsten (W), lanthanum (La), scandium (Sc), gallium (Ga), zinc (Zn), hafnium (Hf), molybdenum (Mo), or any combination thereof.

18. The metal-containing film includes a first region and a second region, The second etching rate at which the etching composition etches the second region is faster than the first etching rate at which the etching composition etches the first region, The method for etching a metal-containing film according to claim 16, wherein the etching step is performed by bringing at least a part of the first region and at least a part of the second region into contact with the etching composition.

19. The method for etching a metal-containing film according to claim 18, wherein the first region contains molybdenum and the second region contains titanium nitride (TiN).

20. Preparing a substrate provided with a metal-containing film; Performing an etching step using the etching composition according to any one of claims 1 to 15 on the metal-containing film to remove at least a part of the metal-containing film; Performing subsequent manufacturing process(es) to fabricate a semiconductor device; A method for manufacturing a semiconductor device, comprising:

Images