ETCHING COMPOSITION, METHOD OF ETCHING METAL-CONTAINING LAYER BY USING THE SAME, AND METHOD OF MANUFACTURING SEMICONDUCTOR DEVICE BY USING THE ETCHING COMPOSITION

Abstract

An etching composition may include an oxidizing agent, an accelerator, an ammonium salt, and an aqueous solvent, wherein the accelerator may include one or more compounds represented by Formula 1, and the ammonium salt may include at least one compound having a structure in which at least one of hydrogen ions (H.sup.+) of a hydroxyl group (*OH) or a thiol group (*SH) included in the accelerator is substituted with an ammonium cation (NH.sub.4.sup.+):

##STR00001##

Formula 1 is as described in the present specification.

Claims

1. An etching composition comprising: an oxidizing agent; an accelerator; an ammonium salt; and an aqueous solvent, wherein the accelerator includes one or more compounds represented by Formula 1 below, and the ammonium salt includes at least one compound having a structure in which at least one of hydrogen ions (H.sup.+) of a hydroxyl group (*OH) or a thiol group (*SH) included in the accelerator is substituted with an ammonium cation (NH.sub.4.sup.+); ##STR00040## wherein, in Formula 1, X.sub.1 and Y.sub.1 are each independently O or S, L.sub.1 is a single bond, a cyclic group having 2 to 10 carbon atoms unsubstituted or substituted with at least one R.sub.0, *C(R.sub.11)(R.sub.12)**, *C(O)**, *C(S)**, *N(R.sub.11)**, *O**, or *S**, n1 is an integer from 1 to 50, when n1 is 2 or more, two or more of L.sub.1 are the same or different from each other, R.sub.1, R.sub.11, R.sub.12 and R.sub.0 are each independently: hydrogen, deuterium, *F, *Cl, *Br, *I, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *NHC(O)(NH.sub.2), or *NHC(S)(NH.sub.2); or a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.1-C.sub.20 alkoxy group, a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20 heteroaryl group, each unsubstituted or substituted with deuterium, *F, *Cl, *Br, *I, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *NHC(O)(NH.sub.2), *NHC(S)(NH.sub.2), or any combination thereof, when a second carbon directly bonded to a first carbon to which a hydroxyl group is bonded exists in Formula 1, a hydroxyl group (*OH) and a thiol group (*SH) are not bonded to the second carbon, and when a fourth carbon directly bonded to a third carbon to which a thiol group is bonded exists in Formula 1, a hydroxyl group (*OH) and a thiol group (*SH) are not bonded to the fourth carbon.

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

3. The etching composition of claim 1, wherein an amount of the oxidizing agent is 1 wt % to 50 wt %, based on 100 wt % of the etching composition.

4. The etching composition of claim 1, wherein in Formula 1, L.sub.1 is a cyclic group having 2 to 10 carbon atoms unsubstituted or substituted with at least one R.sub.0, and n1 is 1.

5. The etching composition of claim 1, wherein L.sub.1 in Formula 1 is a cyclopentane group, a cyclohexane group, a cycloheptane group, a cyclooctane group, a cyclopentene group, a cyclohexene group, a cycloheptene group, a cyclooctene group, a cyclopentadiene group, a benzene group, a cycloheptadiene group, a cyclooctadiene group, a pyrrolidine group, a tetrahydrofuran group, a tetrahydrothiophene group, a piperidine group, a tetrahydro-2H-pyran group, a tetrahydro-2H-thiopyran group, an azepane group, an oxepane group, a thiepane group, a 2,3-dihydro-1H-pyrrole group, a 2,3-dihydrofuran group, a 2,3-dihydrothiophene group, a 2,5-dihydro-1H-pyrrole group, a 2,5-dihydrofuran group, a 2,5-dihydrothiophene group, a pyrrole group, a furan group, a thiophene group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, or a triazine group, each unsubstituted or substituted with at least one R.sub.0.

6. The etching composition of claim 1, wherein in Formula 1, L.sub.1 is a single bond, *C(R.sub.11)(R.sub.12)**, *C(O)**, *C(S)**, *N(R.sub.11)*, *O**, or *S**, and n1 is an integer from 1 to 20.

7. The etching composition of claim 1, wherein R.sub.1, R.sub.11, R.sub.12, and R.sub.0 are each independently: hydrogen, *F, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), or *C(S)(NH.sub.2); or a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.1-C.sub.20 alkoxy group, a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20 heteroaryl group, each unsubstituted or substituted with *F, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), or any combination thereof.

8. The etching composition of claim 1, wherein the compound represented by Formula 1 includes one of compounds represented by Formulae 11 to 19, or any combination thereof: ##STR00041## ##STR00042## wherein, in Formulae 11 to 19, X.sub.1, X.sub.2, Y.sub.1, Y.sub.2, X.sub.3, Y.sub.3, X.sub.4, and Y.sub.4 are each independently O or S, L.sub.1 to L.sub.5 each independently are a single bond, a cyclic group having 2 to 10 carbon atoms unsubstituted or substituted with at least one R.sub.0, *C(R.sub.11)(R.sub.12)**, *C(O)**, *C(S)**, *N(R.sub.11)**, *O**, or *S**, a1 to a5 are each independently an integer from 1 to 15, R.sub.1, R.sub.11 R.sub.12, R.sub.13, R.sub.14 and R.sub.0 are each independently: hydrogen, deuterium, *F, *Cl, *Br, *I, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *NHC(O)(NH.sub.2), or *NHC(S)(NH.sub.2); or a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.1-C.sub.20 alkoxy group, a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20 heteroaryl group, each unsubstituted or substituted with deuterium, *F, *Cl, *Br, *I, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *NHC(O)(NH.sub.2), *NHC(S)(NH.sub.2), or any combination thereof, and T.sub.11 to T.sub.18 are each independently: hydrogen, deuterium, *F, *Cl, *Br, *I, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *NHC(O)(NH.sub.2), or *NHC(S)(NH.sub.2); or a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.1-C.sub.20 alkoxy group, a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20 heteroaryl group, each unsubstituted or substituted with deuterium, *F, *Cl, *Br, *I, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *NHC(O)(NH.sub.2), *NHC(S)(NH.sub.2), or any combination thereof.

9. The etching composition of claim 8, wherein in Formulae 11 to 19, L.sub.1 to L.sub.5 are each independently a single bond, *C(R.sub.11)(R.sub.12)*, *C(O)*, *C(S)*, *N(R.sub.11)*, *O*, or *S*, and T.sub.11 to T.sub.18 are each independently: hydrogen, *F, or *NH.sub.2; or a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.1-C.sub.20 alkoxy group, a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20 heteroaryl group, each unsubstituted or substituted with *F, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), or any combination thereof.

10. The etching composition of claim 1, wherein the compound represented by Formula 1 includes one of compounds represented by Formulae 110 to 129, or any combination thereof: ##STR00043## ##STR00044## ##STR00045## wherein, in Formulae 110 to 129, X.sub.1 and Y.sub.1 are each independently O or S, R.sub.1 and R.sub.0 are each independently: hydrogen, deuterium, *F, *Cl, *Br, *I, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *NHC(O)(NH.sub.2), or *NHC(S)(NH.sub.2); or a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.1-C.sub.20 alkoxy group, a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20 heteroaryl group, each unsubstituted or substituted with deuterium, *F, *Cl, *Br, *I, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *NHC(O)(NH.sub.2), *NHC(S)(NH.sub.2), or any combination thereof, b9 is an integer from 0 to 9, b8 is an integer from 0 to 8, b6 is an integer from 0 to 6, b5 is an integer from 0 to 5, b4 is an integer from 0 to 4, b3 is an integer from 0 to 3, b2 is an integer from 0 to 2, and T.sub.11 is one of: hydrogen, deuterium, *F, *Cl, *Br, *I, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *NHC(O)(NH.sub.2), or *NHC(S)(NH.sub.2); or a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.1-C.sub.20 alkoxy group, a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20 heteroaryl group, each unsubstituted or substituted with deuterium, *F, *Cl, *Br, *I, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *NHC(O)(NH.sub.2), *NHC(S)(NH.sub.2), or any combination thereof.

11. The etching composition of claim 10, wherein in Formulae 110 to 129, T.sub.11 is: hydrogen, *F, or *NH.sub.2; or a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.1-C.sub.20 alkoxy group, a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20 heteroaryl group, each unsubstituted or substituted with *F, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), or any combination thereof.

12. The etching composition of claim 1, wherein an amount of the accelerator is 0.001 wt % to 20 wt %, based on 100 wt % of the etching composition.

13. The etching composition of claim 1, wherein the ammonium salt includes one or more compounds represented by Formula 2: ##STR00046## wherein, in Formula 2, X.sub.1 and Y.sub.1 are each independently O or S, L.sub.1 is a single bond, a cyclic group having 2 to 10 carbon atoms unsubstituted or substituted with at least one R.sub.0, *C(R.sub.11)(R.sub.12)**, *C(O)**, *C(S)**, *N(R.sub.11)**, *O** or *S**, n1 is an integer from 1 to 50, when n1 is 2 or more, two or more of L.sub.1 are the same or different from each other, R.sub.1, R.sub.11, R.sub.12 and R.sub.0 are each independently: hydrogen, deuterium, *F, *Cl, *Br, *I, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *NHC(O)(NH.sub.2), *NHC(S)(NH.sub.2), *ONH.sub.4, *SNH.sub.4, *C(O)ONH.sub.4, *C(S)ONH.sub.4, *C(O)SNH.sub.4, or *C(S)SNH.sub.4; or a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.1-C.sub.20 alkoxy group, a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20 heteroaryl group, each unsubstituted or substituted with deuterium, *F, *Cl, *Br, *I, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *NHC(O)(NH.sub.2), *NHC(S)(NH.sub.2), *ONH.sub.4, *SNH.sub.4, *C(O)ONH.sub.4, *C(S)ONH.sub.4, *C(O)SNH.sub.4, *C(S)SNH.sub.4, or any combination thereof, when a second carbon directly bonded to a first carbon to which a hydroxyl group is bonded exists in Formula 2, a hydroxyl group (*OH) and a thiol group (*SH) are not bonded to the second carbon, and when a fourth carbon directly bonded to a third carbon to which a thiol group is bonded exists in Formula 2, a hydroxyl group (*OH) and a thiol group (*SH) are not bonded to the fourth carbon.

14. The etching composition of claim 1, wherein an amount of the ammonium salt is 0.5 wt % to 20 wt %, based on 100 wt % of the etching composition.

15. The etching composition of claim 1, wherein the ammonium salt includes two or more different compounds of compounds having a structure in which at least one of the hydrogen ions (H.sup.+) of a hydroxyl group (*OH) or a thiol group (*SH) included in the accelerator is substituted with an ammonium cation (NH.sub.4.sup.+).

16. A method of etching a metal-containing layer, the method comprising: preparing a substrate including a metal-containing layer thereon; and performing an etching process on the metal-containing layer by using the etching composition of claim 1 to remove at least a portion of the metal-containing layer.

17. The method of claim 16, wherein 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 any combination thereof.

18. The method of claim 16, wherein the metal-containing layer includes a first region and a second region, the performing the etching process on the metal-containing layer includes etching at least a portion of the first region of the metal-containing layer at a first etch rate using the etching composition and etching at least a portion of the second region of the metal-containing layer at a second etch rate using the etching composition, and the second etch rate is greater than the first etch rate.

19. The method of claim 18, wherein the first region includes aluminum oxide, and the second region includes titanium nitride (TiN), titanium nitride further including aluminum (TiAlN), or any combination thereof.

20. A method of manufacturing a semiconductor device, the method comprising: preparing a substrate including a metal-containing layer thereon; performing an etching process on the metal-containing layer using the etching composition of claim 1, the etching process removing at least a portion of the metal-containing layer; and performing one or more subsequent manufacturing processes to manufacture the semiconductor device.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The above and other aspects, features, and advantages of certain embodiments will be more apparent from the following description taken in conjunction with the accompanying drawings, in which:

[0021] FIG. 1 illustrates a process flow diagram of an embodiment of a method of manufacturing a semiconductor device; and

[0022] FIGS. 2 and 3 are diagrams briefly explaining an embodiment of a method of etching a metal-containing layer.

DETAILED DESCRIPTION

[0023] Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described below, by referring to the figures, to explain aspects of the present description. As used herein, the term and/or includes any and all combinations of one or more of the associated listed items. Expressions such as at least one of, when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list. For example, at least one of A, B, and C, and similar language (e.g., at least one selected from the group consisting of A, B, and C) may be construed as A only, B only, C only, or any combination of two or more of A, B, and C, such as, for instance, ABC, AB, BC, and AC.

[0024] When the terms about or substantially are used in this specification in connection with a numerical value, it is intended that the associated numerical value includes a manufacturing or operational tolerance (e.g., 10%) around the stated numerical value. Moreover, when the words generally and substantially are used in connection with geometric shapes, it is intended that precision of the geometric shape is not required but that latitude for the shape is within the scope of the disclosure. Further, regardless of whether numerical values or shapes are modified as about or substantially, it will be understood that these values and shapes should be construed as including a manufacturing or operational tolerance (e.g., 10%) around the stated numerical values or shapes. When ranges are specified, the range includes all values therebetween such as increments of 0.1%.

To-be-Etched Layer

[0025] The to-be-etched layer may include a metal-containing layer.

[0026] Accordingly, the etching composition may be used in an etching process and/or chemical mechanical polishing (CMP) process for the metal-containing layer.

[0027] Metal contained in the metal-containing layer may include an alkali metal (for example, sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), etc.), an alkaline earth metal (for example, beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), etc.), a lanthanum group metal (for example, lanthanum (La), europium (Eu), terbium (Tb), ytterbium (Yb), etc.), a transition metal (for example, 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 metal (for example, aluminum (Al), gallium (Ga), indium (In), thallium (TI), tin (Sn), bismuth (Bi), etc.), or any combination thereof.

[0028] According to an 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.

[0029] 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.

[0030] For example, the metal-containing layer may include aluminum, titanium, lanthanum, tungsten, molybdenum, or any combination thereof.

[0031] In some embodiments, the metal-containing layer may include titanium.

[0032] In some embodiments, the metal-containing layer may include titanium and aluminum.

[0033] The metal-containing layer may include metal, metal nitride, metal oxide, metal oxynitride, or any combination thereof.

[0034] The metal-containing layer may include metal, metal nitride, metal oxide, metal oxynitride, or any combination thereof, and the metal contained in each of the metal, metal nitride, metal oxide, and metal oxynitride may include indium (In), titanium (Ti), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), zinc (Zn), hafnium (Hf), or any combination thereof.

[0035] The metal-containing layer may include metal nitride. The metal included in the metal nitride may include indium, titanium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof.

[0036] In some embodiments, 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. In some embodiments, the metal-containing layer may include titanium nitride (TiN), titanium nitride further including aluminum (for example, titanium aluminum nitride or TiAlN), titanium nitride further including lanthanum, etc.

[0037] In some embodiments, the metal-containing layer may include 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 (for example, Al.sub.2O.sub.3), indium gallium zinc oxide (IGZO), etc.

[0038] In some embodiments, the metal-containing layer may include the metal and the metal nitride.

[0039] In some embodiments, the metal-containing layer may include, in addition to metal, metalloids (for example, boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium. (Te), etc.), non-metals (for example, nitrogen (N), phosphorus (P), oxygen (O), sulfur(S), selenium (Se), etc.), and any combination thereof.

[0040] For example, the metal-containing layer may further include silicon oxide.

[0041] The metal-containing layer may have a single-layer structure including one or more types of materials, or a multi-layer structure or three-dimensional pattern structure including different materials.

[0042] According to an embodiment, the metal-containing layer includes a first region and a second region, and a second etch rate at which the etching composition etches the second region may be greater than a first etch rate at which the etching composition etches the first region. During the etching process and/or polishing process for 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 since the second etch rate is greater than the first etch rate, the second region may be etched faster than the first region.

[0043] For example, the first region may include metal, metal oxide (for example, aluminum oxide), silicon oxide, or any combination thereof.

[0044] According to an embodiment, the first region may include aluminum oxide.

[0045] In some embodiments, the second region may include metal nitride.

[0046] In some embodiments, the second region may include i) titanium nitride (TiN), ii) titanium nitride further including indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof (for example, TiAlN), or iii) any combination thereof.

[0047] In some embodiments, the first region and the second region may each include i) titanium nitride, ii) titanium nitride further including indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof (for example, TiAlN), or iii) any combination thereof.

[0048] In some embodiments, the first region may include aluminum, and the second region may not include aluminum.

[0049] In some embodiments, the first region may include aluminum oxide, and the second region may include i) titanium nitride (TiN), ii) titanium nitride further including indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof (for example, TiAlN), or iii) any combination thereof.

[0050] In some embodiments, the first region may include aluminum oxide, and the second region may include titanium nitride (TiN), titanium nitride further including aluminum (TiAlN), or any combination thereof.

[0051] In some embodiments, the first region may include an aluminum oxide layer, and the second region may include a titanium nitride layer (TiN layer), a titanium nitride layer further including aluminum (for example, a titanium aluminum nitride layer, or TiAlN layer), or any combination thereof.

[0052] In some embodiments, the first region may be an aluminum oxide layer, and the second region may be a titanium nitride layer (TiN layer) or a titanium nitride layer further including aluminum (for example, a titanium aluminum nitride layer or a TiAlN layer).

[0053] In some embodiments, the first region may include titanium nitride further including aluminum (for example, TiAlN), and the second region may include titanium nitride (TiN).

[0054] In some embodiments, the first region may include a titanium nitride layer further including aluminum (for example, a TiAlN layer), and the second region may include titanium nitride layer (TiN layer).

[0055] In some embodiments, the first region may be a titanium nitride layer further including aluminum (for example, TiAlN layer), and the second region may be a titanium nitride layer (TiN layer).

[0056] The wording a layer is etched as used herein may refer to the feature in which at least some of the materials constituting the layer are removed.

Etching Composition

[0057] The etching composition may include an oxidizing agent, an accelerator, an ammonium salt, and an aqueous solvent.

[0058] The etching composition may be used in the etching process and/or CMP process of the to-be-etched layer, for example, a metal-containing layer described herein.

[0059] According to an embodiment, the etching composition may consist of the oxidizing agent, the accelerator, the ammonium salt, and the aqueous solvent.

Oxidizing Agent

[0060] The oxidizing agent may etch the metal-containing layer and may include, for example, hydrogen peroxide.

[0061] The amount (weight) of the oxidizing agent may be, for example, about 1 wt % to about 50 wt %, about 5 wt % to about 30 wt %, about 10 wt % to about 25 wt %, or about 15 wt % to about 25 wt %, based on 100 wt % of the etching composition.

Aqueous Solvent

[0062] The aqueous solvent is clearly distinguished from various organic solvents and may include, for example, water (for example, deionized water).

[0063] According to an embodiment, the aqueous solvent may be water.

[0064] In some embodiments, the etching composition may not include an organic solvent.

Accelerator

[0065] The accelerator may promote etching of the metal-containing layer by chelating with metal atoms in the metal-containing layer.

[0066] The accelerator may include at least one of compounds represented by Formula 1. For example, the accelerator may include one type of compound of the compounds represented by Formula 1 below:

##STR00003## [0067] wherein X.sub.1 and Y.sub.1 in Formula 1 may each independently be O or S.

[0068] For example, each of X.sub.1 and Y.sub.1 may be O. [0069] L.sub.1 in Formula 1 may be a single bond, a cyclic group having 2 to 10 carbon atoms unsubstituted or substituted with at least one R.sub.0, *C(R.sub.11)(R.sub.12)**, *C(O)**, *C(S)**, *N(R.sub.11)**, *O** or *S**.

[0070] n1 in Formula 1 represents the number of L.sub.1, and n1 may be an integer from 1 to 50. When n1 is 2 or more, two or more of L.sub.1 may be the same or different from each other. For example, n1 may be 1 to 40, 1 to 30, 1 to 20, or 1 to 10.

[0071] According to an embodiment, in Formula 1, L.sub.1 may be a cyclic group having 2 to 10 carbon atoms unsubstituted or substituted with at least one R.sub.0, and n1 may be 1.

[0072] In some embodiments, L.sub.1 in Formula 1 may be a saturated or unsaturated 5-membered to saturated or unsaturated 8-membered carbocyclic group having 5 to 8 carbon atoms, or a saturated or unsaturated 5-membered to saturated or unsaturated 8-membered heterocyclic group having 2 to 7 carbon atoms, each unsubstituted or substituted with at least one R.sub.0.

[0073] In some embodiments, L.sub.1 in Formula 1 may be a cyclopentane group, a cyclohexane group, a cycloheptane group, a cyclooctane group, a cyclopentene group, a cyclohexene group, a cycloheptene group, a cyclooctene group, a cyclopentadiene group, a benzene group, a cycloheptadiene group, a cyclooctadiene group, a pyrrolidine group, a tetrahydrofuran group, a tetrahydrothiophene group, a piperidine group, a tetrahydro-2H-pyran group, a tetrahydro-2H-thiopyran group, an azepane group, an oxepane group, a thiepane group, a 2,3-dihydro-1H-pyrrole group, a 2,3-dihydrofuran group, a 2,3-dihydrothiophene group, a 2,5-dihydro-1H-pyrrole group, a 2,5-dihydrofuran group, a 2,5-dihydrothiophene group, a pyrrole group, a furan group, a thiophene group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, or a triazine group, each unsubstituted or substituted with at least one R.sub.0.

[0074] In some embodiments, in Formula 1, L.sub.1 may be a single bond, *C(R.sub.11)(R.sub.12)*, *C(O)**, *C(S)**, *N(R.sub.11)**, *O**, or *S*, and n1 may be an integer from 1 to 20. For example, in Formula 1, [0075] i) L.sub.1 may be a single bond, or [0076] ii) L.sub.1 may be *C(R.sub.11)(R.sub.12)**, or [0077] iii) at least one of n1 L.sub.1 may each independently be *C(O)**, *C(S)**, *N(R.sub.11)**, *O*, and *S**.

[0078] R.sub.1, R.sub.11, R.sub.12 and R.sub.0 in Formula 1 may each independently be: [0079] hydrogen, deuterium, *F, *Cl, *Br, *I, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *NHC(O)(NH.sub.2), or *NHC(S)(NH.sub.2); or [0080] a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.1-C.sub.20 alkoxy group, a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20 heteroaryl group (for example, a C.sub.1-C.sub.10 alkyl group, a C.sub.1-C.sub.10 alkoxy group, a phenyl group, a naphthyl group, a pyridinyl group, etc.), each unsubstituted or substituted with deuterium, *F, *Cl, *Br, *I, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *NHC(O)(NH.sub.2), *NHC(S)(NH.sub.2), or any combination thereof. R.sub.0 may not be a hydrogen.

[0081] For example, R.sub.1, R.sub.11, R.sub.12, and R.sub.0 may each independently be: [0082] hydrogen, *F, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), or *C(S)(NH.sub.2); or [0083] a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.1-C.sub.20 alkoxy group, a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20 heteroaryl group (for example, a C.sub.1-C.sub.10 alkyl group, a C.sub.1-C.sub.10 alkoxy group, a phenyl group, a naphthyl group, or a pyridinyl group, etc.), each unsubstituted or substituted with *F, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), or any combination thereof.

[0084] In Formula 1, [0085] ii) in the case where a second carbon directly bonded to a first carbon to which a hydroxyl group is bonded exists in Formula 1, a hydroxyl group (*OH) and a thiol group (*SH) are not bonded to the second carbon, and [0086] i) in the case where a fourth carbon directly bonded to a third carbon to which a thiol group is bonded exists in Formula 1, a hydroxyl group (*OH) and a thiol group (*SH) are not bonded to the fourth carbon.

[0087] Accordingly, the cyclometallated ring, which can be formed by chelating the accelerator with the metal atom of the metal-containing layer, may not become a 5-membered cyclometallated ring in which the metal atom of the metal-containing layer is bonded to an oxygen atom or a sulfur atom. Therefore, the etch rate ratio of the metal-containing layer can be more effectively controlled.

[0088] According to an embodiment, the compound represented by Formula 1 may include one of compounds represented by Formulae 11 to 19, or any combination thereof:

##STR00004##

[0089] In Formulae 11 to 19, [0090] the description of each of X.sub.1, Y.sub.1, L.sub.1, R.sub.1, R.sub.11 and R.sub.12 is the same as the description of each of X.sub.1, Y.sub.1, L.sub.1, R.sub.1, R.sub.11, and R.sub.12 in Formula 1 of this specification, X.sub.2, Y.sub.2, X.sub.3, Y.sub.3, X.sub.4, and Y.sub.4 may each independently be O or S, [0091] the description of each of L.sub.2 to L.sub.5 is the same as the description of L.sub.1 of Formula 1 in this specification, [0092] a1 to a5 may each independently be an integer from 1 to 15, [0093] the description of each of R.sub.13 and R.sub.14 is the same as the description of R.sub.11 in Formula 1 in this specification, and [0094] the description of each of T.sub.11 to T.sub.18 is the same as the description of R.sub.11 of Formula 1 in this specification, but each of T.sub.11 to T.sub.18 is not a hydroxyl group or a thiol group.

[0095] For example, in formulae 11 to 19,

[0096] L.sub.1 to L.sub.5 may each independently be a single bond, *C(R.sub.11)(R.sub.12)*, *C(O)**, C(S)**, *N(R.sub.11)**, *O*, or *S*).

[0097] T.sub.11 to T.sub.18 may each independently be: [0098] hydrogen, *F, or *NH.sub.2; or [0099] a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.1-C.sub.20 alkoxy group, a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20 heteroaryl group, each unsubstituted or substituted with *F, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), or any combination thereof.

[0100] According to an embodiment, the compound represented by Formula 1 may include one of compounds represented by Formulae 110 to 129, or any combination thereof:

##STR00005## ##STR00006## ##STR00007##

[0101] In Formulae 110 to 129, [0102] the description of each of X.sub.1, Y.sub.1, R.sub.1, and R.sub.0 is the same as the description of each of X.sub.1, Y.sub.1, R.sub.1, and R.sub.0 in Formula 1. [0103] b9 may be an integer from 0 to 9, [0104] b8 may be an integer from 0 to 8, [0105] b6 may be an integer from 0 to 6, [0106] b5 may be an integer from 0 to 5, [0107] b4 may be an integer from 0 to 4, [0108] b3 may be an integer from 0 to 3, [0109] b2 may be an integer from 0 to 2, and [0110] the description of T.sub.11 is the same as the description of R.sub.11 of Formula 1 in this specification, but T.sub.11 is not a hydroxyl group or a thiol group.

[0111] For example, in Formulae 110 to 129, [0112] T.sub.11 may be: [0113] hydrogen, *F, or *NH.sub.2; or [0114] a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.1-C.sub.20 alkoxy group, a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20 heteroaryl group, each unsubstituted or substituted with *F, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), or any combination thereof.

[0115] The amount (weight) of the accelerator may be, based on 100 wt % of the etching composition, about 0.001 wt % to about 20 wt %, about 0.001 wt % to about 15 wt %, about 0.001 wt % to about 10 wt %, about 0.001 wt % to about 7 wt %, about 0.001 wt % to about 5 wt %, about 0.001 wt % to about 4 wt %, about 0.001 wt % to about 3 wt %, about 0.001 wt % to about 2 wt %, about 0.001 wt % to about 1 wt %, about 0.001 wt % to about 0.5 wt %, about 0.001 wt % to about 0.1 wt %, about 0.005 wt % to about 20 wt %, about 0.005 wt % to about 15 wt %, about 0.005 wt % to about 10 wt %, about 0.005 wt % to about 7 wt %, about 0.005 wt % to about 5 wt %, about 0.005 wt % to about 4 wt %, about 0.005 wt % to about 3 wt %, about 0.005 wt % to about 2 wt %, about 0.005 wt % to about 1 wt %, about 0.005 wt % to about 0.5 wt %, about 0.005 wt % to about 0.1 wt %, about 0.01 wt % to about 20 wt %, about 0.01 wt % to about 15 wt %, about 0.01 wt % to about 10 wt %, about 0.01 wt % to about 7 wt %, about 0.01 wt % to about 5 wt %, about 0.01 wt % to about 4 wt %, about 0.01 wt % to about 3 wt %, about 0.01 wt % to about 2 wt %, about 0.01 wt % to about 1 wt %, about 0.01 wt % to about 0.5 wt %, about 0.01 wt % to about 0.1 wt %, about 0.05 wt % to about 20 wt %, about 0.05 wt % to about 15 wt %, about 0.05 wt % to about 10 wt %, about 0.05 wt % to about 7 wt %, about 0.05 wt % to about 5 wt %, about 0.05 wt % to about 4 wt %, about 0.05 wt % to about 3 wt %, about 0.05 wt % to about 2 wt %, about 0.05 wt % to about 1 wt %, about 0.05 wt % to about 0.5 wt %, or about 0.05 wt % to about 0.1 wt %. When the amount of the accelerator satisfies the range described above, the stability of the etching composition may be obtained.

Ammonium Salt

[0116] The ammonium salt may etch the metal-containing layer.

[0117] The ammonium salt may include at least one of compounds having a structure in which at least one of the hydrogen ions (H.sup.+) of a hydroxyl group (*OH) or a thiol group (*SH) included in the accelerator is substituted with an ammonium cation (NH.sub.4.sup.+). Accordingly, the etch rate and pH of the metal-containing layer of the etching composition may be more effectively controlled.

[0118] In addition, since the ammonium salt includes at least one of compounds having a structure in which at least one of the hydrogen ions (H.sup.+) of a hydroxyl group (*OH) or a thiol group (*SH) included in the accelerator is substituted with an ammonium cation (NH.sub.4.sup.+), the etch rate ratio may not be substantially changed even when the etching composition is used after being stored at a high temperature (for example, about 70 C.) (for example, stored for 24 hours). As such, the etching composition can have excellent high-temperature stability, and thus, the process efficiency of a semiconductor device manufacturing method using an etching and/or CMP process using the etching composition can be improved.

[0119] According to an embodiment, the ammonium salt may include at least one of compounds represented by Formula 2:

##STR00008## [0120] wherein, in Formula 2, [0121] X.sub.1 and Y.sub.1 may each independently be O or S, [0122] L.sub.1 may be a single bond, a cyclic group having 2 to 10 carbon atoms unsubstituted or substituted with at least one R.sub.0, *C(R.sub.11)(R.sub.12)**, *C(O)**, *C(S)**, *N(R.sub.11)**, *O** or *S**, [0123] n1 may be an integer from 1 to 50, [0124] when n1 is 2 or more, two or more of L.sub.1 may be the same or different from each other, [0125] R.sub.1, R.sub.11, R.sub.12, and R.sub.0 may each independently be: [0126] hydrogen, deuterium, *F, *Cl, *Br, *I, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *NHC(O)(NH.sub.2), *NHC(S)(NH.sub.2), *ONH.sub.4, *SNH.sub.4, *C(O)ONH.sub.4, *C(S)ONH.sub.4, *C(O)SNH.sub.4, or *C(S)SNH.sub.4; or [0127] a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.1-C.sub.20 alkoxy group, a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20 heteroaryl group, each unsubstituted or substituted with deuterium, *F, *Cl, *Br, *I, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *NHC(O)(NH.sub.2), *NHC(S)(NH.sub.2), *ONH.sub.4, *SNH.sub.4, *C(O)ONH.sub.4, *C(S)ONH.sub.4, *C(O)SNH.sub.4, *C(S)SNH.sub.4, or any combination thereof, [0128] i) in the case where a second carbon directly bonded to a first carbon to which a hydroxyl group is bonded exists in Formula 2, a hydroxyl group (*OH) and a thiol group (*SH) are not bonded to the second carbon, and [0129] ii) in the case where a fourth carbon directly bonded to a third carbon to which a thiol group is bonded exists in Formula 2, a hydroxyl group (*OH) and a thiol group (*SH) are not bonded to the fourth carbon.

[0130] For descriptions of L.sub.1 and n1 in Formula 2, refer to the descriptions of L.sub.1 and n1 in Formula 1, respectively.

[0131] According to an embodiment, the compound represented by Formula 2 may include one of compounds represented by Formulae 21, 22, 23, 23(1), 24, 24(1), 25, 26, 26(1), 26(2), 27, 27(1), 28, 29, 29(1), 29(2), 29(3) and 29(4), or any combination thereof:

##STR00009## ##STR00010## ##STR00011##

[0132] In Formulae 21, 22, 23, 23(1), 24, 24(1), 25, 26, 26(1), 26(2), 27, 27(1), 28, 29, 29(1), 29(2), 29(3), and 29(4), [0133] the description of each of X.sub.1, Y.sub.1, L.sub.1, R.sub.1, R.sub.11 and R.sub.12 is the same as the description of each of X.sub.1, Y.sub.1, L.sub.1, R.sub.1, R.sub.11, and R.sub.12 in Formula 2 of this specification, [0134] X.sub.2, Y.sub.2, X.sub.3, Y.sub.3, X.sub.4, and Y.sub.4 may each independently be O or S, [0135] the description of each of L.sub.2 to L.sub.5 is the same as the description of L.sub.1 of Formula 2 in this specification, [0136] a1 to a5 may each independently be an integer from 1 to 15, [0137] the description of each of R.sub.13 and R.sub.14 is the same as the description of R.sub.11 in Formula 2 in this specification, and [0138] the description of each of T.sub.11 to T.sub.18 is the same as the description of R.sub.11 of Formula 2 in this specification, but each of T.sub.11 to T.sub.18 is not a hydroxyl group or a thiol group.

[0139] For example, in Formulae 21, 22, 23, 23(1), 24, 24(1), 25, 26, 26(1), 26(2), 27, 27(1), 28, 29, 29(1), 29(2), 29(3), and 29(4), [0140] L.sub.1 to L.sub.5 may each independently be a single bond, *C(R.sub.11)(R.sub.12)**, *C(O)**, *C(S)**, *N(R.sub.11)**, *O**, or *S**.

[0141] T.sub.11 to T.sub.18 may each independently be: [0142] hydrogen, *F, or *NH.sub.2; or [0143] a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.1-C.sub.20 alkoxy group, a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20 heteroaryl group, each unsubstituted or substituted with *F, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *ONH.sub.4, *SNH.sub.4, *C(O)ONH.sub.4, *C(S)ONH.sub.4, *C(O)SNH.sub.4, *C(S)SNH.sub.4, or any combination thereof.

[0144] In some embodiments, the compound represented by Formula 2 may include one of compounds represented by Formulae 210 to 229, or any combination thereof:

##STR00012##

[0145] In Formulae 210 to 229, [0146] the description of each of X.sub.1, Y.sub.1, R.sub.1, and R.sub.0 is the same as the description of each of X.sub.1, Y.sub.1, R.sub.1, and R.sub.0 in Formula 2, [0147] b9 may be an integer from 0 to 9, [0148] b8 may be an integer from 0 to 8, [0149] b6 may be an integer from 0 to 6, [0150] b5 may be an integer from 0 to 5, [0151] b4 may be an integer from 0 to 4, [0152] b3 may be an integer from 0 to 3, [0153] b2 may be an integer from 0 to 2, and [0154] the description of T.sub.11 is the same as the description of R.sub.11 of Formula 2 in this specification, but T.sub.11 is not a hydroxyl group or a thiol group.

[0155] For example, in Formulae 210 to 229, [0156] T.sub.11 may be: [0157] hydrogen, *F, or *NH.sub.2; or [0158] a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.1-C.sub.20 alkoxy group, a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20 heteroaryl group, each unsubstituted or substituted with *F, *OH, *SH, *NH.sub.2, *C(O) H, *C(S)H, *C(O)OH, *C(S)OH, *C(O)SH, *C(S)SH, *C(O)(NH.sub.2), *C(S)(NH.sub.2), *ONH.sub.4, *SNH.sub.4, *C(O)ONH.sub.4, *C(S)ONH.sub.4, *C(O)SNH.sub.4, *C(S)SNH.sub.4, or any combination thereof.

[0159] The amount (weight) of the ammonium salt may be, based on 100 wt % of the etching composition, about 0.5 wt % to about 20 wt %, about 0.5 wt % to about 10 wt %, about 1 wt % to about 20 wt %, about 0.5 wt % to about 10 wt %, about 1 wt % to about 7 wt %, or about 1 wt % to about 5 wt %.

[0160] In some embodiments, the ammonium salt may include different two or more of compounds having a structure in which at least one of the hydrogen ions (H.sup.+) of a hydroxyl group (*OH) or a thiol group (*SH) included in the accelerator is substituted with an ammonium cation (NH.sub.4.sup.+). For example, the combination 1.sub.com1 in Table 1 below may be referred to.

[0161] In some embodiments, the ammonium salt may further include NH.sub.4OH, tetramethylammonium hydroxide, etc., in addition to compounds having a structure in which at least one of the hydrogen ions (H.sup.+) of a hydroxyl group (*OH) or a thiol group (*SH) included in the accelerator included in the etching composition is substituted with an ammonium cation (NH.sub.4.sup.+).

Specific Examples of Accelerators and Ammonium Salts

[0162] The accelerator may include, for example, one of Compounds A1 to A29:

##STR00013## ##STR00014## ##STR00015## ##STR00016##

[0163] Compounds A1 to A29 satisfy the condition i) in the case where a second carbon directly bonded to a first carbon to which a hydroxyl group is bonded exists in Formula 1, a hydroxyl group (*OH) and a thiol group (*SH) are not bonded to the second carbon, and the condition ii) in the case where a fourth carbon directly bonded to a third carbon to which a thiol group is bonded exists in Formula 1, a hydroxyl group (*OH) and a thiol group (*SH) are not bonded to the fourth carbon. For understanding, the first carbon, the second carbon, the third carbon, and the fourth carbon of Compounds A1 to A29 are indicated with 1, 2, 3, and 4, respectively, as shown below:

##STR00017## ##STR00018## ##STR00019##

[0164] In addition, the ammonium salt may include, for example, at least one of Compounds S1 to S29, S1(1), S2(1), S3(1), S16(1), S18(1), S18(2), S20(1), S20(2), S20 (3), S20 (4), S24(1), S25(1), and S26 (1):

##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025##

[0165] The ammonium salt contained in the etching composition includes a compound having structure in which at least one of the hydrogen ions (H.sup.+) of the hydroxyl group (*OH) or thiol group (*SH) contained in the accelerator is substituted with an ammonium cation (NH.sub.4.sup.+). Accordingly, the combination of an accelerator and an ammonium salt included in the etching composition may be one of the combinations listed in Table 1 below:

TABLE-US-00001 TABLE 1 Combination No. Accelerator Ammonium salt 1 A1 S1 2 A2 S2 3 A3 S3 4 A4 S4 5 A5 S5 6 A6 S6 7 A7 S7 8 A8 S8 9 A9 S9 10 A10 S10 11 A11 S11 12 A12 S12 13 A13 S13 14 A14 S14 15 A15 S15 16 A16 S16 17 A17 S17 18 A18 S18 19 A19 S19 20 A20 S20 21 A21 S21 22 A22 S22 23 A23 S23 24 A24 S24 25 A25 S25 26 A26 S26 27 A27 S27 28 A28 S28 29 A29 S29 1(1) A1 S1(1) 1.sub.com1 A1 S1 and S1(1) 2(1) A2 S2(1) 2.sub.com1 A2 S2 and S2(1) 3(1) A3 S3(1) 3.sub.com1 A3 S3 and S3(1) 16(1) A16 S16(1) 16.sub.com1 A16 S16 and S16(1) 18(1) A18 S18(1) 18(2) A18 S18(2) 18.sub.com1 A16 S18 and S18(1) 18.sub.com2 A16 S18 and S18(2) 18.sub.com3 A16 S18, S18(1), and S18(2) 20(1) A20 S20(1) 20(2) A20 S20(2) 20(3) A20 S20(3) 20(4) A20 S20(4) 20.sub.com1 A20 S20 and S20(1) 20.sub.com2 A20 S20 and S20(2) 20.sub.com3 A20 S20 and S20(3) 20.sub.com4 A20 S20 and S20(4) 20.sub.com5 A20 S20(1) and S20(2) 20.sub.com6 A20 S20(1) and S20(3) 20.sub.com7 A20 S20(1) and S20(4) 20.sub.com8 A20 S20(2) and S20(3) 20.sub.com9 A20 S20(2) and S20(4) 20.sub.com10 A20 S20(3) and S20(4) 20.sub.com11 A20 S20, S20(1) and S20(2) 20.sub.com12 A20 S20, S20(1) and S20(3) 20.sub.com13 A20 S20, S20(1) and S20(4) 20.sub.com14 A20 S20, S20(2) and S20(3) 20.sub.com15 A20 S20, S20(2) and S20(4) 20.sub.com16 A20 S20, S20(3) and S20(4) 20.sub.com17 A20 S20(1), S20(2) and S20(3) 20.sub.com18 A20 S20(1), S20(2), and S20(4) 20.sub.com19 A20 S20(1), S20(3), and S20(4) 20.sub.com20 A20 S20(2), S20(3), and S20(4) 20.sub.com21 A20 S20, S20(1), S20(2), and S20(3) 20.sub.com22 A20 S20, S20(1), S20(2), and S20(4) 20.sub.com23 A20 S20, S20(1), S20(3), and S20(4) 20.sub.com24 A20 S20, S20(2), S20(3), and S20(4) 20.sub.com25 A20 S20(1), S20(2), S20(3), and S20(4) 20.sub.com26 A20 S20, S20(1), S20(2), S20(3), and S20(4) 24(1) A24 S24(1) 24.sub.com1 A24 S24 and S24(1) 25(1) A25 S25(1) 25.sub.com1 A25 S25 and S25(1) 26(1) A26 S26(1) 26.sub.com1 A26 S26 and S26(1)

[0166] The etching composition may have a pH of about 1 to about 7, for example, about 2 to about 6. When the etching composition has these ranges of pH, chelating between the accelerator and ammonium salt and the metal, as described later, can be more effectively achieved.

[0167] According to an embodiment, the etching composition may be used in a metal-containing layer etching process and/or a CMP process. The metal-containing layer is as described in the present specification.

[0168] In some embodiments, the etching composition may 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 cleaner for a packaging process, a wafer adhesive remover, an etchant, a post-etch residue stripper, an ash residue cleaner, a photoresist (PR) residue stripper, a CMP cleaner, or a post-CMP cleaner.

[0169] Metal-containing layer etching method and semiconductor device manufacturing method

[0170] A metal-containing layer can be more effectively etched using the etching composition described above.

[0171] Referring to FIG. 1, an embodiment of the method of etching a metal-containing layer includes: preparing a substrate provided with a metal-containing layer thereon (S100); and performing an etching process on the metal-containing layer using the etching composition as described in this specification to remove at least a portion of the metal-containing layer (S110).

[0172] The metal-containing layer is as described in the present specification.

[0173] 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.

[0174] In some embodiments, the metal-containing layer may include metal, metal nitride, metal oxide, metal oxynitride, or any combination thereof.

[0175] Due to the inclusion of a combination of the accelerator and the ammonium salt as described above, the etching composition may have a more effectively controlled etching selectivity for the metal-containing layer, thereby increasing the efficiency, accuracy, and productivity of the etching process. Therefore, a semiconductor device with excellent performance can be manufactured by using a metal-containing layer etching process using the etching composition described above.

[0176] FIGS. 2 and 3 are diagrams briefly explaining an embodiment of a method of etching a metal-containing layer 120.

[0177] Referring to FIG. 2, a substrate 100 provided with the metal-containing layer 120 thereon is provided. The interlayer 110 may be disposed between the substrate 100 and the metal-containing layer 120. Although not shown in FIG. 2, circuit elements (for example, transistor gates, metal lines, impurity regions, and/or semiconductor layers) may be disposed, for example, inside the substrate 100, on the substrate 100, and/or between the substrate 100 and the interlayer 110. According to an embodiment, the metal-containing layer 120 may be disposed directly on the substrate 100 and the interlayer 110 may be omitted.

[0178] The metal-containing layer 120 may include a first region 121 and a second region 122. A second etch rate at which the etching composition etches the second region 122 may be greater than a first etch rate at which the etching composition etches the first region 121.

[0179] Referring to FIG. 3, the etching composition is used to etch the metal-containing layer 120 to etch at least a portion of the first region 121 and at least a portion of the second region 122 to form a pattern of the metal-containing layer 125. The etching process may be performed by contacting each of at least a portion of the first region 121 and at least a portion of the second region 122 with the etching composition.

[0180] The etching composition may etch at least a portion of the first region 121 and at least a portion of the second region 122. In FIG. 3, the pattern of the metal-containing layer 125 formed after etching may include at least a portion of the second region 122, but if necessary, the embodiment may be variously modified, for example, the etching process may be performed to completely remove the second region 122 of the pattern of the metal-containing layer 125.

[0181] In some embodiments, the first region 121 may include metal oxide (for example, aluminum oxide), silicon oxide, or any combination thereof.

[0182] In some embodiments, the second region 122 may include metal nitride (for example, titanium nitride).

[0183] In some embodiments, the second region 122 may include i) titanium nitride (TiN), ii) titanium nitride further including indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof (for example, TiAlN), or iii) any combination thereof.

[0184] In some embodiments, the first region 121 and the second region 122 may each include i) titanium nitride (TiN), ii) titanium nitride further including indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof (for example, TiAlN), or iii) any combination thereof.

[0185] In some embodiments, the first region 121 may include aluminum, and the second region 122 may not include aluminum.

[0186] In some embodiments, the first region 121 may include aluminum oxide, and the second region 122 may include i) titanium nitride (TiN), ii) titanium nitride further including indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof (for example, TiAlN), or iii) any combination thereof.

[0187] In some embodiments, the first region 121 may include aluminum oxide, and the second region 122 may include titanium nitride (TiN), titanium nitride further including aluminum (TiAlN), or any combination thereof.

[0188] In some embodiments, the first region 121 may include an aluminum oxide layer, and the second region 122 may include a titanium nitride layer (TiN layer), a titanium nitride layer further including aluminum (for example, a titanium aluminum nitride layer, or TiAlN layer), or any combination thereof.

[0189] In some embodiments, the first region 121 may be an aluminum oxide layer, and the second region 122 may be a titanium nitride layer (TiN layer) or a titanium nitride layer further including aluminum (for example, a titanium aluminum nitride layer or a TiAlN layer).

[0190] In some embodiments, the first region 121 may include titanium nitride further including aluminum (for example, TiAlN), and the second region 122 may include titanium nitride (TiN).

[0191] In some embodiments, the first region 121 may include a titanium nitride layer further including aluminum (for example, a TiAlN layer), and the second region 122 may include titanium nitride layer (TiN layer).

[0192] In some embodiments, the first region 121 may be a titanium nitride layer further including aluminum (for example, TiAlN layer), and the second region 122 may be a titanium nitride layer (TiN layer).

[0193] In some embodiments, the etch rate ratio of the second region 122 to the first region 121 of the etching composition may be about 110 to about 700, about 150 to about 700, about 200 to about 700, about 255 to about 700, about 110 to about 600, about 150 to about 600, about 200 to about 600, about 255 to about 600, about 110 to about 500, about 150 to about 500, about 200 to about 500, about 255 to about 500, about 110 to about 440, about 150 to about 440, about 200 to about 440, or about 255 to about 440. The etch rate ratio of the second region 122 to the first region 121 may be obtained by dividing the second etch rate at which the etching composition etches the second region 122 by the first etch rate at which the etching composition etches the first region 121. When the etch rate ratio of the second region 122 to the first region 121 of the etching composition satisfies the range described above, the efficiency and productivity of the etching process can be improved.

[0194] In some embodiments, the first region 121 includes aluminum oxide, the second region 122 includes titanium nitride or titanium nitride further including aluminum, and the etch rate ratio of the second region 122 with respect to the first region 121 of the etching composition may be about 110 to about 700, about 150 to about 700, about 200 to about 700, about 255 to about 700, about 110 to about 600, about 150 to about 600, about 200 to about 600, about 255 to about 600, about 110 to about 500, about 150 to about 500, about 200 to about 500, about 255 to about 500, about 110 to about 440, about 150 to about 440, about 200 to about 440, or about 255 to about 440.

[0195] Referring to FIG. 1, a method of manufacturing semiconductor device according to an embodiment includes preparing a substrate provided with a metal-containing layer thereon (S100); performing an etching process on the metal-containing layer using the etching composition to remove at least a portion of the metal-containing layer (S110); and performing a subsequent process to manufacture a semiconductor device (S120).

[0196] Hereinafter, one or more example 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 inventive concepts. Examples 1 to 6 and Comparative Examples A to D

[0197] The materials shown in Tables 2 and 3 below were mixed in the amounts shown in Tables 2 and 3 to prepare etching compositions for Examples 1 to 6 and Comparative Examples A to D. Hydrogen peroxide was used as an oxidizing agent for each etching composition, and the remainder corresponds to water (deionized water).

Evaluation Example 1 (Etching Rate Ratio Evaluation)

[0198] The etching composition of Example 1 was placed in two beakers and heated to 70 C., and then a 1 cm1 cm titanium aluminum nitride layer (TiAlN layer) specimen and a 1 cm1 cm aluminum oxide layer specimen were immersed in respective beakers for 5 minutes. Then, the thickness of each of the titanium aluminum nitride layer and the aluminum oxide layer was measured using an ellipsometer (M-2000, JAWoolam), a four-point resistance meter, and X-ray fluorescence (XRF) spectrometer, so as to evaluate each of the etch rate for the titanium aluminum nitride layer and the etch rate for the aluminum oxide layer (/min) of the etching composition of Example 1. Next, the etch rate for the titanium aluminum nitride layer was divided by the etch rate for the aluminum oxide layer to evaluate the R (TiAlN/AlO) of the etching composition of Example 1. Results thereof are summarized in Table 2.

[0199] This test was repeatedly carried out using each of the etching compositions of Example 2, Example 3, and Comparative Example A. Results thereof are summarized in Table 2.

TABLE-US-00002 TABLE 2 TiAIN Oxidizing layer Aluminum agent Accelerator Ammonium salt etch oxide R Amount Amount Amount rate etch rate (TIAIN/ (wt % ) Material (wt %) Material (wt %) (/min) (/min) AIO) Example 1 20 A1 0.05 S1 3 40 0.1 400 (Combination 1) Example 2 20 A3 0.05 S3 3 44 0.1 440 (Combinationtion 3) Example 3 20 A19 0.05 S19 3 51 0.2 255 (Combinationtion 19) Comparative 20 AR 0.05 SR 3 84 0.8 105 example A [00026][00027][00028][00029][00030][00031][00032][00033]

[0200] From Table 2, it can be seen that the etching compositions of Examples 1 to 3 have an excellent etch rate ratio compared to the etching composition of Comparative Example A.

Evaluation Example 2 (High-Temperature Stability Evaluation)

[0201] R(TiAlN/AlO) of the etching composition of Example 4 was evaluated using the same method as Evaluation Example 1. This is referred to as R.sub.0 hr of the etching composition of Example 4.

[0202] The etching composition of Example 4 was placed in two beakers and heated to 70 C., and then a 1 cm1 cm titanium aluminum nitride layer (TiAlN layer) specimen and a 1 cm1 cm aluminum oxide layer specimen were immersed in respective beakers for 24 hours. Then, the thickness of each of the titanium aluminum nitride layer and the aluminum oxide layer was measured using an ellipsometer (M-2000, JAWoolam), a four-point resistance meter, and XRF, so as to evaluate each of the etch rate for the titanium aluminum nitride layer and the etch rate for the aluminum oxide layer (/min) of the etching composition of Example 4. Then, the etch rate for the titanium aluminum nitride film was divided by the etch rate for the aluminum oxide film, to evaluate the R(TiAlN/AlO) of the etching composition of Example 4 stored at high temperature for 24 hours. This is referred to as R.sub.24 hr of the etching composition of Example 4.

[0203] From this, [(R.sub.0 hr-R.sub.24 hr)/R.sub.0 hr]100(%) of the etching composition 4 was calculated to evaluate the change rate (%) of the etch rate ratio before and after high temperature storage of the etching composition of Example 4. Results thereof are summarized in Table 3.

[0204] This test was repeatedly carried out using each of the etching compositions of Comparative Example B, Example 5, Comparative Example C, Example 6, and Comparative Example D. Results thereof are summarized in Table 3.

TABLE-US-00003 TABLE 3 Oxidizing High temperature agent Accelerator Ammonium salt stability amount amount amount (etch rate ratio change (wt %) material (wt %) material (wt %) rate, %) Example 4 20 A2 0.05 S2 3 2.4% (Combination 2) Comparative 20 A2 0.05 Ammonium 3 4.3% Example B acetate Example 5 20 A11 0.05 S11 3 2.1% (Combination 11) Comparative 20 A11 0.05 Ammonium 3 3.9% example C acetate Example 6 20 A13 0.05 S13 3 3.5% (Combination 13) Comparative 20 A13 0.05 Ammonium 3 6.8% example D acetate [00034][00035][00036][00037][00038][00039]

[0205] From Table 3, the etching compositions of Example 4, Example 5, and Example 6 each have a lower etch rate ratio change rate than each of the etching compositions of Comparative Example B, Comparative Example C, and Comparative Example D. Accordingly, it can be confirmed that the etching compositions of the present disclosure has excellent high temperature stability.

[0206] The etching composition has more effectively controlled etching selectivity and, at the same time, high-temperature stability, for the metal-containing layer that is the etching target layer. Accordingly, the efficiency, accuracy, and productivity of the etching process can be increased. Therefore, by using the etching composition, a more effective etching process and/or CMP process can be performed on the to-be-etched layer. Therefore, a semiconductor device manufactured using a metal-containing layer etching process using the etching composition can have excellent performance.

[0207] It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments. While one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.