Composition, method for treating metal-containing film, and method for manufacturing electronic device

Abstract

Provided are a composition, a method of treating a metal-containing film using the composition, and a method of manufacturing an electronic device by using the composition, the composition including an oxidizing agent, phosphoric acid, an organic acid, and an etching control agent and having a pH of 2.0 or less, in which the oxidizing agent includes hydrogen peroxide, an iodine-containing compound, or any combination thereof, the etching control agent includes a hydroxyl group-free and nitrogen-containing compound, the hydroxyl group-free and nitrogen-containing compound includes a compound represented by Formula 5, a compound represented by Formula 6, or any combination thereof, and the groups in Formulae 5 and 6 are as described in the specification.

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit of Korean Patent Application No. 10-2024-0133255, filed on September 30, 2024, and Korean Patent Application No. 10-2025-0134991, filed on September 19, 2025, the disclosures of which are incorporated herein by reference in their entirety. Technical Field

[0003] This disclosure relates to compositions, methods of treating metal-containing films using them, and / or methods of manufacturing electronic devices using them. Background Technology

[0004] To meet consumer demands for superior performance and low cost, there is increasing research into improvements in the integration density and reliability of various electronic devices, such as semiconductor devices. However, as the integration density of semiconductor devices increases, damage to components during the manufacturing process has a significant impact on the device's reliability and electrical characteristics. In particular, during the manufacturing process of semiconductor devices, films (e.g., metal-containing films) undergo various processing techniques such as etching, cleaning, and polishing. Therefore, there is a persistent need for compositions with appropriate etching rates, etc., to more effectively implement metal-containing film processing techniques. Summary of the Invention

[0005] The invention provides compositions capable of more effectively controlling the etching rate of various metal-containing films, methods for treating metal-containing films using said compositions, and methods for manufacturing electronic devices using said compositions.

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

[0007] According to one aspect of this disclosure, a method for processing a metal-containing film may include:

[0008] Prepare a substrate (substrate) comprising the metal-containing film, the metal-containing film comprising a first region and a second region; and

[0009] The metal-containing film is brought into contact with the composition;

[0010] The first region and the second region may independently include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), cobalt (Co), copper (Cu), or any combination thereof.

[0011] This includes the fact that the material in the first region may be different from the material included in the second region.

[0012] The composition may include an oxidant, phosphoric acid, an organic acid, and an etching control agent.

[0013] The oxidant may include hydrogen peroxide, iodine-containing compounds, or any combination thereof.

[0014] The etching control agent may include a nitrogen-containing compound that does not contain hydroxyl groups.

[0015] The hydroxyl-free and nitrogen-containing compound may include compounds represented by Formula 5, compounds represented by Formula 6, or any combination thereof, and

[0016] The composition may have a pH of 2 or less.

[0017] Formula 5

[0018] T 52 -[(L5) a5 ]-T 51

[0019] Formula 6

[0020] CY6-[L6-N(R 61 (R) 62 )] a6

[0021] In Equation 5, L5 can be *-C(Z) 51 (Z) 52 )-*'、*-N(Z 53 )-*', or *-C(=O)-*',

[0022] In Equation 5, a5 can be an integer from 2 to 30.

[0023] In Equation 5, T 51 It can be *-N(R) 51 (R) 52 ), and T 52 For *-N(R) 53 (R) 54 ),

[0024] In Formula 6, the ring CY6 can be a saturated or unsaturated carbocyclic group having 5 to 15 carbon atoms, a saturated heterocyclic group having 2 to 15 carbon atoms, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a carbazole group, a dibenzofuran group, or a dibenzothiophene group.

[0025] In Equation 6, L6 can be a single bond or a C1-C bond. 30Alkylene

[0026] In Equation 6, a6 can be an integer from 1 to 5.

[0027] In equations 5 and 6, Z 51 Z 52 Z 53 R 51 R 52 R 53 R 54 R 61 and R 62 Each can be independently:

[0028] Hydrogen or amino; or

[0029] Unsubstituted or amino- or mono(C1-C) 30 alkyl)amino, di(C1-C) 30 Alkyl)amino, *-C(=O)-N(Q) 51 (Q) 52 C1-C replaced by, or any combination thereof 30 alkyl,

[0030] Q 51 and Q 52 Each can be independently:

[0031] Hydrogen; or

[0032] Unsubstituted or amino- or mono(C1-C) 30 alkyl)amino, di(C1-C) 30 alkyl)amino, or any combination thereof substituted C1-C 30 Alkyl groups, and

[0033] * and *' can each indicate the binding site with adjacent atoms.

[0034] In some embodiments, the first region may include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), or any combination thereof, and

[0035] The second region may include tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

[0036] In some embodiments, the first region may include a metal nitride, a metal oxynitride, or any combination thereof, and

[0037] The second region may include conductive metal.

[0038] In some embodiments, the first region may include titanium nitride, titanium oxynitride, or any combination thereof, and the titanium nitride and the titanium oxynitride may each optionally further include indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

[0039] In some embodiments, the etching area ratio (which may be a ratio obtained by dividing the first area of ​​the first region exposed to contact with the composition by the second area of ​​the second region exposed to contact with the composition) may be in the range of about 0.05 to about 1.0.

[0040] In some embodiments, based on 100% by weight of the composition, the amount of phosphoric acid in the composition may be from about 10% by weight to about 85% by weight.

[0041] In some implementations, in Equation 5, i) each L5 can be *-C(Z) 51 (Z) 52 )-*'and a5 can be an integer from 2 to 11, or ii) each L5 is *-C(Z 51 (Z) 52 )-*' or *-N(Z 53 )-*'and a5 is an integer from 5 to 11, and

[0042] In Formula 6, cycloCY6 can be a cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclopentene group, cyclohexene group, cycloheptene group, cyclooctene group, phenyl group, naphthyl group, piperazine group, pyrrolidinyl group, piperidine group, azacycloheptyl group, tetrahydrofuran group, tetrahydrothiophene group, tetrahydro-2H-pyran group, tetrahydro-2H-thioran group, 4H-pyran-4-one group, pyridine group, pyrimidine group, pyrazine group, pyridazine group, triazine group, carbazole group, dibenzofuran group, or dibenzothiophene group.

[0043] In some embodiments, the composition may have a pH of about -3.0 to about 1.0.

[0044] According to one aspect of this disclosure, a method for manufacturing an electronic device including transistors is provided. The method may include:

[0045] Forming a structure comprising source and drain electrodes spaced apart from each other and electrically connected to the channel; and

[0046] A gate electrode and a gate insulating film are provided on the structure, wherein the gate insulating film is located between the gate electrode and the channel.

[0047] The gate electrode can be provided through the following:

[0048] Provide a barrier layer including metal nitrides, metal oxynitrides, or any combination thereof;

[0049] Provides a conductive layer comprising a conductive metal; and

[0050] The gate electrode is formed by contacting the barrier layer and the conductive layer with the composition to etch a portion of the barrier layer and a portion of the conductive layer;

[0051] The composition may include an oxidant, phosphoric acid, an organic acid, and an etching control agent.

[0052] The oxidant may include hydrogen peroxide, iodine-containing compounds, or any combination thereof.

[0053] The etching control agent may include a nitrogen-containing compound that does not contain hydroxyl groups.

[0054] The hydroxyl-free and nitrogen-containing compound may include compounds represented by Formula 5, compounds represented by Formula 6, or any combination thereof, and

[0055] The composition may have a pH of 2 or lower.

[0056] Formula 5

[0057] T 52 -[(L5) a5 ]-T 51

[0058] Formula 6

[0059] CY6-[L6-N(R 61 (R) 62 )] a6

[0060] In Equation 5, L5 can be *-C(Z) 51 (Z) 52 )-*'、*-N(Z 53 )-*', or *-C(=O)-*',

[0061] In Equation 5, a5 can be an integer from 2 to 30.

[0062] In Equation 5, T 51 It can be *-N(R) 51 (R) 52 ), and T 52 It can be *-N(R) 53 (R) 54 ),

[0063] In Formula 6, the ring CY6 can be a saturated or unsaturated carbocyclic group having 5 to 15 carbon atoms, a saturated heterocyclic group having 2 to 15 carbon atoms, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a carbazole group, a dibenzofuran group, or a dibenzothiophene group.

[0064] In Equation 6, L6 can be a single bond or a C1-C bond. 30 Alkylene

[0065] In Equation 6, a6 can be an integer from 1 to 5.

[0066] In equations 5 and 6, Z 51 Z 52 Z 53 R 51 R 52 R 53 R 54 R 61 and R 62 Each independently is:

[0067] Hydrogen or amino; or

[0068] Unsubstituted or modified by amino groups, mono(C1-C) 30 alkyl)amino, di(C1-C) 30 Alkyl)amino, *-C(=O)-N(Q) 51 (Q) 52 C1-C replaced by, or any combination thereof 30 alkyl,

[0069] Q 51 and Q 52 Each independently is:

[0070] Hydrogen; or

[0071] Unsubstituted or modified by amino groups, mono(C1-C) 30 alkyl)amino, di(C1-C) 30 alkyl)amino, or any combination thereof substituted C1-C 30 Alkyl groups, and

[0072] * and *' can each indicate the binding site with adjacent atoms.

[0073] In some embodiments, the barrier layer may include titanium nitride, titanium oxynitride, or any combination thereof.

[0074] The titanium nitride and titanium oxynitride may each optionally further comprise indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof, and

[0075] The conductive layer may include tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

[0076] In some embodiments, the method may further include:

[0077] After forming the gate electrode by contacting the barrier layer and the conductive layer with the composition to etch a portion of the barrier layer and a portion of the conductive layer to form an etched barrier layer and an etched conductive layer, an insulating layer is provided on the surface of the etched barrier layer and the surface of the etched conductive layer.

[0078] According to one aspect of this disclosure, the composition comprises:

[0079] Oxidizing agents, phosphoric acid, organic acids, and etching control agents,

[0080] The oxidant may include hydrogen peroxide, iodine-containing compounds, or any combination thereof.

[0081] The etching control agent may include a nitrogen-containing compound that does not contain hydroxyl groups.

[0082] The hydroxyl-free and nitrogen-containing compound may include compounds represented by Formula 5, compounds represented by Formula 6, or any combination thereof, and

[0083] The composition may have a pH of 2 or lower.

[0084] Formula 5

[0085] T 52 -[(L5) a5 ]-T 51

[0086] Formula 6

[0087] CY6-[L6-N(R 61 (R) 62 )] a6

[0088] in,

[0089] In Equation 5, L5 can be *-C(Z) 51 (Z) 52 )-*'、*-N(Z 53 )-*', or *-C(=O)-*',

[0090] In Equation 5, a5 can be an integer from 2 to 30.

[0091] In Equation 5, T 51 It can be *-N(R) 51 (R) 52 ), and T52 It can be *-N(R) 53 (R) 54 ),

[0092] In Formula 6, the ring CY6 can be a saturated or unsaturated carbocyclic group having 5 to 15 carbon atoms, a saturated heterocyclic group having 2 to 15 carbon atoms, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a carbazole group, a dibenzofuran group, or a dibenzothiophene group.

[0093] In Equation 6, L6 can be a single bond or a C1-C bond. 30 Alkylene

[0094] In Equation 6, a6 can be an integer from 1 to 5.

[0095] In equations 5 and 6, Z 51 Z 52 Z 53 R 51 R 52 R 53 R 54 R 61 and R 62 Each independently is:

[0096] Hydrogen or amino; or

[0097] Unsubstituted or modified by amino groups, mono(C1-C) 30 alkyl)amino, di(C1-C) 30 Alkyl)amino, *-C(=O)-N(Q) 51 (Q) 52 C1-C replaced by, or any combination thereof 30 alkyl,

[0098] Q 51 and Q 52 Each independently is:

[0099] Hydrogen; or

[0100] Unsubstituted or modified by amino groups, mono(C1-C) 30 alkyl)amino, di(C1-C) 30 alkyl)amino, or any combination thereof substituted C1-C 30 Alkyl groups, and

[0101] * and *' each represent a binding site with an adjacent atom.

[0102] According to another aspect of this disclosure, a method for processing a metal-containing film includes:

[0103] Prepare a substrate having a metal-containing film comprising a first region and a second region thereon, and

[0104] The metal-containing film is brought into contact with the composition.

[0105] The first region and the second region independently include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), cobalt (Co), copper (Cu), or any combination thereof, and

[0106] The material included in the first region may be different from the material included in the second region.

[0107] According to another aspect of this disclosure, a method for manufacturing an electronic device including transistors is provided.

[0108] The transistor may include:

[0109] Ditch,

[0110] The source and drain electrodes are spaced apart from each other and electrically connected to the channel.

[0111] Gate electrode, and

[0112] A gate insulating film disposed between the gate electrode and the channel, and

[0113] The method may include:

[0114] Provide a barrier layer including metal nitrides, metal oxynitrides, or any combination thereof;

[0115] Provides a conductive layer comprising a conductive metal; and

[0116] The gate electrode is formed by contacting the barrier layer and the conductive layer with the composition to etch a portion of the barrier layer and a portion of the conductive layer. Attached Figure Description

[0117] The above and other aspects, features, and advantages of some embodiments of this disclosure will become more apparent from the following description taken in conjunction with the accompanying drawings, wherein:

[0118] Figure 1A and 2 This is a schematic diagram illustrating a method for processing metal-containing films.

[0119] Figure 1B It indicates that it can contact composition 30. Figure 1A A schematic diagram of the surface of the metal-containing film 20A;

[0120] Figure 3 and 4This is a schematic diagram illustrating other embodiments of a method for processing metal-containing films;

[0121] Figure 5 It is a schematic plan view of the electronic device according to the embodiment;

[0122] Figure 6A yes Figure 5 A perspective view of one embodiment of the electronic device shown;

[0123] Figure 6B yes Figure 5 A perspective view of another embodiment of the electronic device shown;

[0124] Figures 7 to 9 It is a brief description of the manufacturing process. Figure 6A A schematic diagram of a portion of the process of the transistor structure shown;

[0125] Figure 10 It is a process flow diagram illustrating the implementation of a method for manufacturing electronic devices;

[0126] Figure 11A These are the 1H NMR data for compound A1 after it has been mixed with a high concentration (70 wt%) of phosphoric acid and heated at a high temperature (60 °C).

[0127] Figure 11B The data are 1H NMR of PEI after it has been mixed with a high concentration (70 wt%) of phosphoric acid and heated at a high temperature (60 °C).

[0128] Figure 12 This is a transmission electron microscope (TEM) image of sample 1, in which a molybdenum film and a titanium nitride film are arranged between two silicon oxide films;

[0129] Figure 13A These are TEM images of sample 1 immersed in the composition of Example 1; and

[0130] Figure 13B This is a TEM image of sample 1 immersed in the composition of comparative example C2. Detailed Implementation

[0131] The embodiments will now be described in detail, examples of which are illustrated in the accompanying drawings, wherein the same reference numerals always refer to the same elements. In this respect, the embodiments may take different forms and should not be construed as limited to the description set forth herein. Therefore, the embodiments are described below only by reference to the accompanying drawings to illustrate aspects. As used herein, the term “and / or” includes any and all combinations of one or more of the associated enumerated items. Expressions such as “at least one of…” when preceding or following a list of elements modify the entire list of elements and not individual elements of that list. For example, “at least one of A, B, and C” and similar language (e.g., “at least one selected from A, B, and C” and “at least one of A, B, or C”) can be interpreted as only A, only B, only C, or any combination of two or more of A, B, and C, such as ABC, AB, BC, and AC.

[0132] When the terms “about” or “substantially” are used in conjunction with numerical values ​​in this specification, it is intended that the relevant numerical value includes manufacturing or operational tolerances (e.g., ±10%) around the stated numerical value. Furthermore, when the terms “generally” and “substantially” are used in conjunction with geometry, it is intended that precision of the geometry is not required, but tolerances for the shape are within the scope of this disclosure. Additionally, regardless of whether a numerical value or shape is modified to “about” or “substantially”, it will be understood that these values ​​and shapes should be interpreted as including manufacturing or operational tolerances (e.g., ±10%) around the stated numerical value or shape. When a range is specified, the range includes all values ​​within that range, for example, increments of 0.1%.

[0133] Unless otherwise stated, any and all instances and / or exemplary language used herein are intended only to better illustrate the technical concepts and do not constitute a limitation on the scope of the implementation.

[0134] Metal-containing membranes

[0135] Metal-containing films 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.), lanthanides (e.g., lanthanum (La), europium (Eu), terbium (Tb), ytterbium (Yb), etc.), and 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.), later transition metals (e.g., aluminum (Al), gallium (Ga), indium (In), thallium (Tl), tin (Sn), bismuth (Bi), etc.), or any combination thereof.

[0136] According to embodiments, the metal-containing film may include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), cobalt (Co), copper (Cu), or any combination thereof.

[0137] According to another embodiment, the metal-containing film may include two or more different types of metals.

[0138] According to another embodiment, the metal-containing film may include titanium.

[0139] According to another embodiment, the metal-containing film may i) include titanium (Ti), and ii) optionally further include indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), silicon (Si), or any combination thereof, in addition to titanium.

[0140] Metal-containing films may include metals, metal nitrides, metal oxides, metal oxynitrides, or any combination thereof.

[0141] According to embodiments, the metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof, and the metal, the metal of the metal nitride, the metal of the metal oxide, and the metal of the metal oxynitride may each include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), cobalt (Co), copper (Cu), or any combination thereof.

[0142] According to another embodiment, the metal-containing film may include metal nitrides, metal oxynitrides, or any combination thereof as described above (e.g., titanium nitrides, titanium oxynitrides, or any combination thereof).

[0143] According to another embodiment, the metal-containing film may include the metals described above (e.g., conductive metals such as tungsten, molybdenum, and ruthenium).

[0144] According to another embodiment, the metal-containing film may include i) metal nitrides, metal oxynitrides, or any combination thereof as described above (e.g., titanium nitrides, titanium oxynitrides, or any combination thereof) and ii) metals as described above (e.g., conductive metals such as tungsten, molybdenum, and ruthenium).

[0145] According to another embodiment, the metal-containing film may include titanium nitride, titanium oxynitride, or any combination thereof, and may further include tungsten, molybdenum, ruthenium, or any combination thereof in addition to titanium nitride, titanium oxynitride, or any combination thereof. The titanium nitride and titanium oxynitride may each optionally further include indium, aluminum, lanthanum, scandium, gallium, silicon, or any combination thereof.

[0146] According to another embodiment, the metal-containing film may include titanium nitride, further including aluminum titanium nitride (e.g., TiAlN), further including lanthanum titanium nitride, further including silicon titanium nitride (e.g., TiSiN), etc.

[0147] Metal-containing films can be single-layer structures comprising one or more types of materials or multi-layer structures comprising different materials. Multiple films included in a multi-layer structure can be stacked vertically or arranged horizontally relative to a substrate. Single-layer and multi-layer structures can have various three-dimensional patterns (e.g., vias, trenches, etc.).

[0148] According to an embodiment, the metal-containing film includes a first region and a second region, wherein the first region and the second region may independently include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), cobalt (Co), copper (Cu), or any combination thereof, and the material included in the first region may be different from the material included in the second region.

[0149] According to another embodiment, the first region may include titanium.

[0150] According to another embodiment, the first region may i) include titanium (Ti), and ii) optionally further include indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), silicon (Si), or any combination thereof, in addition to titanium.

[0151] According to another embodiment, the second region may include tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

[0152] According to another embodiment, the first region may include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), or any combination thereof, and the second region may include tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

[0153] According to another embodiment, the first region may include a metal nitride, a metal oxynitride, or any combination thereof, and the second region may include a conductive metal.

[0154] For example, the first region may have i) a single-layer structure of a metal nitride film, ii) a single-layer structure of a metal oxynitride film, or iii) a double-layer structure of a metal nitride film and a metal oxynitride film.

[0155] According to another embodiment, the first region may include titanium nitride, titanium oxynitride, or any combination thereof, wherein the titanium nitride and titanium oxynitride may each optionally further include indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

[0156] According to another embodiment, the first region may include titanium nitride, further including aluminum titanium nitride (e.g., TiAlN), further including lanthanum titanium nitride, further including silicon titanium nitride (e.g., TiSiN), etc.

[0157] As used herein, etching of any membrane can refer to the removal of at least a portion of the material constituting the membrane.

[0158] Composition

[0159] The composition may include an oxidant, phosphoric acid, organic acid, and an etching control agent.

[0160] This composition can be used in various processing techniques for metal-containing films as described herein, such as etching, cleaning, and polishing processes.

[0161] The composition may further include a polar solvent (e.g., water).

[0162] According to embodiments, the composition may not include fluorine-containing compounds. Although not intended to be limited by any particular theory, when the composition includes fluorine-containing compounds, adjacent materials (e.g., various oxides, etc.) disposed adjacent to the metal-containing film may be damaged during the processing of metal-containing films using the composition, as described below, leading to degradation of the performance of electronic and / or semiconductor devices.

[0163] According to embodiments, the composition may consist of (or substantially consist of) an oxidant, phosphoric acid, an organic acid, an etching control agent, and a polar solvent (e.g., water). In some embodiments, the composition may include an oxidant, phosphoric acid, an organic acid, and an etching control agent, and the remainder of the composition may be water.

[0164] Oxidizing agent

[0165] The oxidizing agent is used to etch at least a portion of the metal-containing film and may include hydrogen peroxide, an iodine-containing compound, or any combination thereof.

[0166] According to embodiments, the oxidant may include hydrogen peroxide, periodic acid (H5IO6 and / or HIO4), iodic acid (HIO3), or any combination thereof.

[0167] According to embodiments, the oxidant may include at least one of hydrogen peroxide and periodic acid.

[0168] According to another embodiment, the oxidant may include hydrogen peroxide.

[0169] According to another embodiment, the oxidant may include periodic acid.

[0170] According to another embodiment, the oxidant may be hydrogen peroxide.

[0171] According to another embodiment, the oxidant may be periodic acid.

[0172] According to another embodiment, the composition may not include fluorine-containing compounds (e.g., HF, NH4F, etc.) as oxidants. Without being limited by any particular theory, when the composition includes fluorine-containing compounds as oxidants, adjacent materials (e.g., various oxides) arranged adjacent to the metal-containing film can be damaged when the composition is used to treat a metal-containing film, leading to degradation of the performance of electronic and / or semiconductor devices.

[0173] Based on 100% by weight of the composition, the amount (by weight) of the oxidant may be, for example, about 0.001% by weight to about 3% by weight, about 0.001% by weight to about 1% by weight, about 0.001% by weight to about 0.7% by weight, about 0.001% by weight to about 0.5% by weight, about 0.005% by weight to about 3% by weight, about 0.005% by weight to about 1% by weight, about 0.005% by weight to about 0.7% by weight, about 0.005% by weight to about 0.5% by weight, about 0.01% by weight to about 3% by weight, about 0.01% by weight to about 1% by weight, about 0.01% by weight to about 0.7% by weight, about 0.01% by weight to about 0.5% by weight, about 0.02% by weight to about 3% by weight, about 0.02% by weight to about 1% by weight, about 0.02% by weight to about 0.7% by weight, or about 0.02% by weight to about 0.5% by weight.

[0174] According to another embodiment, the oxidant may include hydrogen peroxide, and based on 100% by weight of the composition, the amount (by weight) of hydrogen peroxide may be, for example, about 0.001% by weight to about 3% by weight, about 0.001% by weight to about 1% by weight, about 0.001% by weight to about 0.7% by weight, about 0.001% by weight to about 0.5% by weight, about 0.01% by weight to about 3% by weight, about 0.01% by weight to about 1% by weight, about 0.01% by weight to about 0.7% by weight, about 0.01% by weight to about 0.5% by weight, about 0.02% by weight to about 1% by weight. 3 wt%, about 0.02 wt% to about 1 wt%, about 0.02 wt% to about 0.7 wt%, about 0.02 wt% to about 0.5 wt%, about 0.1 wt% to about 3 wt%, about 0.1 wt% to about 1 wt%, about 0.1 wt% to about 0.7 wt%, about 0.1 wt% to about 0.5 wt%, about 0.3 wt% to about 3 wt%, about 0.3 wt% to about 1 wt%, about 0.3 wt% to about 0.7 wt%, about 0.3 wt% to about 0.5 wt%, or about 0.5 wt% to about 0.7 wt%.

[0175] According to another embodiment, the oxidizing agent may include periodic acid, and based on 100% by weight of the composition, the amount (by weight) of periodic acid may be, for example, about 0.001% by weight to about 3% by weight, about 0.001% by weight to about 1% by weight, about 0.001% by weight to about 0.5% by weight, about 0.001% by weight to about 0.1% by weight, about 0.001% by weight to about 0.05% by weight, about 0.001% by weight to about 0.02% by weight, about 0.005% by weight to about 3% by weight, about 0.005% by weight to about 1% by weight, about 0.005% by weight to about 0.5% by weight, about 0.005% by weight to about 0.1% by weight, about 0.005% by weight. From about 0.05 wt%, about 0.005 wt% to about 0.02 wt%, about 0.01 wt% to about 3 wt%, about 0.01 wt% to about 1 wt%, about 0.01 wt% to about 0.5 wt%, about 0.01 wt% to about 0.1 wt%, about 0.01 wt% to about 0.05 wt%, about 0.01 wt% to about 0.02 wt%, about 0.02 wt% to about 3 wt%, about 0.02 wt% to about 1 wt%, about 0.02 wt% to about 0.5 wt%, about 0.02 wt% to about 0.1 wt%, about 0.02 wt% to about 0.05 wt%, or about 0.02 wt% to about 0.03 wt%.

[0176] Phosphoric acid

[0177] Phosphoric acid can be used, together with an oxidizing agent, to etch at least a portion of a metal-containing film.

[0178] According to embodiments, the composition may not include sulfuric acid, hydrochloric acid, or nitric acid. Without being limited by any particular theory, the stability of the composition may decrease when sulfuric acid, hydrochloric acid, or nitric acid are used with the oxidizing agents described above, making the composition unsuitable for use in metal-containing membrane treatment processes.

[0179] Based on 100% by weight of the composition, the amount (by weight) of phosphoric acid may be, for example, about 10% by weight to about 85% by weight, about 15% by weight to about 85% by weight, about 20% by weight to about 85% by weight, about 25% by weight to about 85% by weight, about 30% by weight to about 85% by weight, about 35% by weight to about 85% by weight, about 40% by weight to about 85% by weight, about 45% by weight to about 85% by weight, about 50% by weight to about 85% by weight, about 55% by weight to about 85% by weight, about 10% by weight to about 80% by weight, about 15% by weight to about 80% by weight, about 20% by weight to about 80% by weight, about 25% by weight to about 80% by weight, about 30% by weight to about 80% by weight, about 35% by weight to about 80% by weight, about 40% by weight to about 80% by weight, about 45% by weight to about 80% by weight, about 50% by weight to about 80% by weight, about 55% by weight to about 80% by weight. 0% by weight, about 10% by weight to about 75% by weight, about 15% by weight to about 75% by weight, about 20% by weight to about 75% by weight, about 25% by weight to about 75% by weight, about 30% by weight to about 75% by weight, about 35% by weight to about 75% by weight, about 40% by weight to about 75% by weight, about 45% by weight to about 75% by weight, about 50% by weight to about 75% by weight, about 55% by weight to about 75% by weight, about 10% by weight to about 70% by weight, about 15% by weight to about 70% by weight, about 20% by weight to about 70% by weight, about 25% by weight to about 70% by weight, about 30% by weight to about 70% by weight, about 35% by weight to about 70% by weight, about 40% by weight to about 70% by weight, about 45% by weight to about 70% by weight, about 50% by weight to about 70% by weight, about 55% by weight to about 70% by weight, or about 60% by weight to about 70% by weight.

[0180] organic acids

[0181] Organic acids can be used to control the etching rate of at least a portion of a metal-containing film.

[0182] Organic acids may include monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, or any combination thereof.

[0183] The number of carbon atoms in monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids can be 1 to 31, 1 to 20, 1 to 10, 1 to 5, or 2 to 3.

[0184] According to the embodiments, the organic acid may include:

[0185] HCOOH;

[0186] Aliphatic compounds having 1 to 30 carbon atoms (e.g., 1 to 20 carbon atoms or 1 to 15 carbon atoms), each substituted with at least one carboxyl group (*-COOH) (e.g., 1, 2, or 3 carboxyl groups); or aromatic compounds having 6 to 30 carbon atoms (e.g., 6 to 15 carbon atoms or 6 to 10 carbon atoms); or

[0187] Any combination thereof,

[0188] In the aliphatic and aromatic compounds, at least one hydrogen atom may optionally be replaced by: hydroxyl, thiol, amino, C1-C 10 Alkyl (e.g., C1-C5 alkyl), C1-C 10 Alkoxy groups (e.g., C1-C5 alkoxy groups), C1-C 10 Alkylthio (e.g., C1-C5 alkylthio), mono(C1-C5) 10 Alkyl)amino (e.g., mono(C1-C5)amino), di(C1-C5)amino 10 Alkyl)amino (e.g., di(C1-C5)amino), phenyl, or any combination thereof.

[0189] According to the embodiments, the aliphatic compound may be a saturated aliphatic compound (e.g., alkanes, cycloalkanes, etc.) or an unsaturated aliphatic compound (e.g., alkenes, alkynes, cycloalkenes, etc.).

[0190] According to another embodiment, the aliphatic compound may be an acyclic aliphatic compound (e.g., alkanes, alkenes, alkynes, etc.) or a cyclic aliphatic compound (e.g., cycloalkanes, cycloalkenes, adamantane, norbenzene, etc.).

[0191] According to another embodiment, the aliphatic compound may be a straight-chain aliphatic compound (e.g., CH3-CH2-CH2-CH2-CH3, etc.) or a branched aliphatic compound (e.g., CH3-CH(CH3)-CH2-CH3, CH3-C(CH3)2-CH3, etc.).

[0192] According to another embodiment, the aromatic compound may be benzene.

[0193] According to another embodiment, the organic acid may include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, gallic acid, succinic acid, malic acid, maleic acid, crotonic acid, fumaric acid, ascorbic acid, glutamic acid, citric acid, tartaric acid, glycolic acid, lactic acid, benzoic acid, salicylic acid, or any combination thereof.

[0194] Based on 100% by weight of the composition, the amount of organic acid may be from about 0.1% by weight to about 15% by weight, from about 0.5% by weight to about 15% by weight, from about 1% by weight to about 15% by weight, from about 3% by weight to about 15% by weight, from about 5% by weight to about 15% by weight, from about 7% by weight to about 15% by weight, from about 0.1% by weight to about 13% by weight, from about 0.5% by weight to about 13% by weight, from about 1% by weight to about 13% by weight, from about 3% by weight to about 13% by weight, from about 5% by weight to about 13% by weight, from about 7% by weight to about 13% by weight, from about 7% by weight to about 10% by weight, or from about 10% by weight to about 13% by weight.

[0195] Etching control agent

[0196] Etching control agents, together with organic acids, can be used to control etching rates, etc., by interacting with various metal atoms in the metal-containing film that is the film to be treated.

[0197] Etching control agents may include nitrogen-containing compounds that do not contain hydroxyl groups. The term "nitrogen-containing compound that does not contain hydroxyl groups" means a compound that does not contain hydroxyl groups and includes at least one nitrogen atom as a molecular component.

[0198] Without being limited by any particular theory, when hydroxyl-containing and nitrogen-containing compounds (e.g., alkanolamines, etc.) are used with oxidants as described above, the high hydrophilicity of the hydroxyl groups in the hydroxyl-containing and nitrogen-containing compounds may prevent them from interacting well with the various metal atoms in the metal-containing film, and therefore effective etching rate control may not be achieved.

[0199] According to another embodiment, the hydroxyl-free and nitrogen-containing compound may include compounds represented by Formula 5 (which include polyalkylene polyamines), compounds represented by Formula 6 (which include amines containing cyclic groups), or any combination thereof (i.e., compounds represented by Formula 5 and compounds represented by Formula 6):

[0200] Formula 5

[0201] T 52 -[(L5) a5 ]-T 51

[0202] Formula 6

[0203] CY6-[L6-N(R 61 (R) 62 )] a6

[0204] In Equation 5, L5 can be *-C(Z) 51 (Z) 52 )-*'、*-N(Z 53)-*', or *-C(=O)-*',

[0205] In Equation 5, a5 can be an integer from 2 to 30.

[0206] In Equation 5, T 51 It can be *-N(R) 51 (R) 52 ), and T 52 It can be *-N(R) 53 (R) 54 ),

[0207] In Formula 6, the ring CY6 can be a saturated or unsaturated carbocyclic group having 5 to 15 carbon atoms, a saturated heterocyclic group having 2 to 15 carbon atoms, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a carbazole group, a dibenzofuran group, or a dibenzothiophene group.

[0208] In Formula 6, L6 can be a single bond or a C1-C30 alkylene group.

[0209] In Equation 6, a6 can be an integer from 1 to 5.

[0210] In equations 5 and 6, Z 51 Z 52 Z 53 R 51 R 52 R 53 R 54 R 61 and R 62 Each can be independently:

[0211] Hydrogen or amino (*-NH2); or

[0212] Unsubstituted or amino- or mono(C1-C) 30 alkyl)amino, di(C1-C) 30 Alkyl)amino, *-C(=O)-N(Q) 51 (Q) 52 C1-C replaced by, or any combination thereof 30 Alkyl groups, and

[0213] Q 51 and Q 52 Each can be independently:

[0214] Hydrogen; or

[0215] Unsubstituted or amino- or mono(C1-C) 30 alkyl)amino, di(C1-C) 30 alkyl)amino, or any combination thereof substituted C1-C 30 Alkyl groups, and

[0216] * and *' each represent a binding site with an adjacent atom.

[0217] According to another implementation, each L5 in Equation 5 can be *-C(Z) 51 (Z) 52 )-*'.

[0218] According to another implementation, each L5 in Equation 5 can be *-C(Z) 51 (Z) 52 )-*' or *-N(Z 53 )-*'.

[0219] According to another implementation, a5 in Formula 5 can be an integer from 2 to 25, an integer from 2 to 20, an integer from 2 to 15, or an integer from 2 to 11.

[0220] According to another implementation, each L5 in Equation 5 can be *-C(Z) 51 (Z) 52 )-*', and a5 can be an integer from 2 to 11.

[0221] According to another implementation, each L5 can be *-C(Z) 51 (Z) 52 )-*' or *-N(Z 53 )-*', and a5 can be an integer from 5 to 11.

[0222] According to another implementation, each L5 can be *-C(Z) 51 (Z) 52 )-*' or *-N(Z 53 )-*', and *-N(Z 53 The number of )-*' can be 1, 2, 3 or 4.

[0223] According to another embodiment, the ring CY6 in Formula 6 may be a saturated or unsaturated carbocyclic group having 5 to 10 carbon atoms, or a saturated heterocyclic group having 2 to 10 carbon atoms.

[0224] According to another embodiment, the cycloCY6 in Formula 6 may be a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclopentene group, a cyclohexene group, a cycloheptene group, a cyclooctene group, a phenyl group, a naphthyl group, a piperazine group, a pyrrolidinyl group, a piperidine group, an azacycloheptyl group, a tetrahydrofuran group, a tetrahydrothiophene group, a tetrahydro-2H-pyran group, a tetrahydro-2H-thioran group, a 4H-pyran-4-one group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a carbazole group, a dibenzofuran group, or a dibenzothiophene group.

[0225] According to another embodiment, L6 in Formula 6 can be a single bond or a C1-C bond. 10 Alkylenes (e.g., C1-C5 alkylenes).

[0226] According to another implementation, a6 in Formula 6 can be 1, 2 or 3.

[0227] According to another implementation, a6 in Formula 6 can be 1 or 2.

[0228] According to another embodiment, in equations 5 and 6, Z 51 Z 52 Z 53 R 51 R 52 R 53 R 54 R 61 and R 62 Each can be independently:

[0229] Hydrogen or amino; or

[0230] Unsubstituted or amino- or mono(C1-C) 30 alkyl)amino, di(C1-C) 10 Alkyl)amino, *-C(=O)-N(Q) 51 (Q) 52 C1-C replaced by, or any combination thereof 10 Alkyl groups, and

[0231] Q 51 and Q 52 Each can be independently:

[0232] Hydrogen; or

[0233] Unsubstituted or amino- or mono(C1-C) 30 alkyl)amino, di(C1-C) 10 alkyl)amino, or any combination thereof substituted C1-C 10 alkyl.

[0234] According to another embodiment, in equations 5 and 6, Z 51 Z 52 Z 53 R 51 R 52 R 53 R 54 R 61 and R 62 Each can be independently:

[0235] Hydrogen or amino; or

[0236] Unsubstituted or modified by amino, mono(C1-C5 alkyl)amino, di(C1-C5 alkyl)amino, *-C(=O)-N(Q) 51 (Q) 52 ), or any combination thereof substituted C1-C5 alkyl groups, and

[0237] Q 51 and Q 52 Each can be independently:

[0238] Hydrogen; or

[0239] C1-C5 alkyl groups that are unsubstituted or substituted with amino, mono(C1-C5 alkyl)amino, di(C1-C5 alkyl)amino, or any combination thereof.

[0240] According to another embodiment, the hydroxyl-free and nitrogen-containing compound may include the compound represented by Formula 51:

[0241] <Formula 51>

[0242] T 52 -{C(Z 51 (Z) 52 )] a51 -N(Z 53 )} b51 -[C(Z 54 (Z) 55 )] a52 -T 51

[0243] In Equation 51,

[0244] T 51 T 52 Z 51 Z 52 and Z 53 Each can be independent as described in this article.

[0245] Z 54 and Z 55 Each can be discussed independently, as in the section on Z in this article. 51 Described,

[0246] a51 and a52 can each be an integer from 2 to 5 (e.g., 2 or 3), and

[0247] b51 can be an integer from 1 to 7 (e.g., 1, 2, or 3).

[0248] According to another embodiment, in formula 51,

[0249] i) a51 and a52 can be 2, and b51 can be 1 (e.g., compounds A1, A4, and A28);

[0250] ii) a51 and a52 can be 2, and b51 can be 2 (e.g., compounds A5 and A6);

[0251] iii) a51 and a52 can be 2, and b51 can be 3 (e.g., compound A2);

[0252] iv) a51 and a52 can be 3, and b51 can be 2 (e.g., compound A22); or

[0253] v) a51 and a52 can be 3, and b51 can be 1 (e.g., compounds A23 and A24).

[0254] According to another embodiment, the hydroxyl-free and nitrogen-containing compound may include the compound represented by Formula 52:

[0255] <Formula 52>

[0256] T 52 -[C(Z 51 (Z) 52 )] a53 -T 51

[0257] In Equation 52,

[0258] T 51 T 52 Z 51 and Z 52 Each can be independently as described in this article, and

[0259] a53 can be an integer from 2 to 25, an integer from 2 to 20, an integer from 2 to 15, or an integer from 2 to 11.

[0260] According to another implementation, in Equation 52, a53 can be an integer from 2 to 11.

[0261] According to another embodiment, in formula 52,

[0262] i) a53 can be 11 (e.g., compound A3);

[0263] ii) a53 can be 2 (e.g., compounds A7, A8, A21, and A27); or

[0264] iii) a53 can be 6 (e.g., compounds A9, A10 and A11).

[0265] According to another embodiment, the hydroxyl-free and nitrogen-containing compound may include the compound represented by Formula 6.

[0266] According to another implementation, in Equation 6,

[0267] i) L6 can be a single bond, and a6 can be 2 (e.g., compounds A12 to A17 and A20);

[0268] ii) L6 can be a single bond, and a6 can be 1 (e.g., compound A18);

[0269] iii) L6 can be a single bond, and a6 can be 3 (e.g., compound A19);

[0270] iv) L6 may be a C3 alkylene group, and a6 may be 2 (e.g., compound A25); or

[0271] v)L6 can be a C3 alkylene group, and a6 can be 1 (e.g., compound A26).

[0272] According to another embodiment, the nitrogen-containing compound that does not contain hydroxyl groups may include at least one of compounds A1 to A28:

[0273]

[0274] .

[0275] Based on 100% by weight of the composition, the amount (by weight) of the etching control agent may be from about 0.01% by weight to about 5% by weight, from about 0.01% by weight to about 4% by weight, from about 0.01% by weight to about 3% by weight, from about 0.01% by weight to about 2% by weight, from about 0.01% by weight to about 1.5% by weight, from about 0.01% by weight to about 1% by weight, from about 0.05% by weight to about 5% by weight, from about 0.05% by weight to about 4% by weight, from about 0.05% by weight to about 3% by weight, from about 0.05% by weight to about 2% by weight, from about 0.05% by weight to about 1.5% by weight, from about 0%. 0.5% by weight to about 1% by weight, about 0.1% by weight to about 5% by weight, about 0.1% by weight to about 4% by weight, about 0.1% by weight to about 3% by weight, about 0.1% by weight to about 2% by weight, about 0.1% by weight to about 1.5% by weight, about 0.1% by weight to about 1% by weight, about 0.5% by weight to about 5% by weight, about 0.5% by weight to about 4% by weight, about 0.5% by weight to about 3% by weight, about 0.5% by weight to about 2% by weight, about 0.5% by weight to about 1.5% by weight, about 0.5% by weight to about 1% by weight, or about 1% by weight to about 1.5% by weight.

[0276] pH

[0277] The composition described above may have a pH of 2.0 or less. For example, the composition described above may have a pH of 1.7 or less, 1.5 or less, 1.3 or less, 1.0 or less, 0.9 or less, 0.7 or less, 0.5 or less, 0.3 or less, 0.1 or less, or 0.0 or less.

[0278] According to embodiments, the composition may have the following pH values: about -3.0 to about 2.0, about -3.0 to about 1.7, about -3.0 to about 1.5, about -3.0 to about 1.3, about -3.0 to about 1.0, about -3.0 to about 0.9, about -3.0 to about 0.7, about -3.0 to about 0.5, about -3.0 to about 0, about -2.5 to about 2.0, about -2.5 to about 1.7, about -2.5 to about 1.5. Approximately -2.5 to approximately 1.3, approximately -2.5 to approximately 1.0, approximately -2.5 to approximately 0.9, approximately -2.5 to approximately 0.7, approximately -2.5 to approximately 0.5, approximately -3.0 to approximately 0, approximately -2.0 to approximately 2.0, approximately -2.0 to approximately 1.7, approximately -2.0 to approximately 1.5, approximately -2.0 to approximately 1.3, approximately -2.0 to approximately 1.0, approximately -2.0 to approximately 0.9, approximately -2.0 to approximately 0.7, approximately -2.0 to approximately 0.5 Approximately -2.0 to approximately 0; approximately -1.5 to approximately 2.0; approximately -1.5 to approximately 1.7; approximately -1.5 to approximately 1.5; approximately -1.5 to approximately 1.3; approximately -1.5 to approximately 1.0; approximately -1.5 to approximately 0.9; approximately -1.5 to approximately 0.7; approximately -1.5 to approximately 0.5; approximately -1.5 to approximately 0; approximately -1.0 to approximately 2.0; approximately -1.0 to approximately 1.7; approximately -1.0 to approximately 1.5; approximately -1.0 to approximately 1.3. The pH values ​​are approximately -1.0 to about 1.0, approximately -1.0 to about 0.9, approximately -1.0 to about 0.7, approximately -1.0 to about 0.5, approximately -1.0 to about 0, approximately -0.6 to about 2.0, approximately -0.6 to about 1.7, approximately -0.6 to about 1.5, approximately -0.6 to about 1.3, approximately -0.6 to about 1.0, approximately -0.6 to about 0.9, approximately -0.6 to about 0.7, approximately -0.6 to about 0.5, or approximately -0.6 to about 0. When the composition has a pH within these ranges, better interaction between the etching control agent and metal atoms in the metal-containing film is achieved.

[0279] According to an embodiment, the composition may include about 0.001% to about 3% by weight of an oxidant, about 10% to about 70% by weight of phosphoric acid, about 0.1% to about 15% by weight of an organic acid, and about 0.01% to about 3% by weight of an etching control agent.

[0280] According to another embodiment, the composition may include about 0.001% to about 3% by weight of an oxidant, about 10% to about 75% by weight of phosphoric acid, about 0.1% to about 13% by weight of an organic acid, and about 0.01% to about 5% by weight of an etching control agent.

[0281] According to another embodiment, the composition may include about 0.001% to about 3% by weight of an oxidant, about 10% to about 70% by weight of phosphoric acid, about 0.1% to about 15% by weight of an organic acid, and about 0.01% to about 5% by weight of an etching control agent.

[0282] According to another embodiment, the composition can be used in metal-containing film processing processes, such as etching, cleaning, or polishing processes for metal-containing films. Metal-containing films can be described as follows.

[0283] Alternatively, the composition may also be used as an etching byproduct remover, a post-etching process byproduct remover, an ashing process byproduct remover, a cleaning composition, a photoresist (PR) remover, an etching composition for packaging processes, a cleaning agent for packaging processes, a wafer adhesive remover, an etchant, a post-etching residue stripper, an ashing residue cleaner, a PR residue stripper, a chemical mechanical polishing (CMP) cleaner, or a post-CMP cleaner.

[0284] Methods for treating metal-containing films

[0285] Using the composition described above, metal-containing films comprising a first region and a second region can be processed more effectively, wherein the material in the first region differs from the material included in the second region. For a description of the metal-containing film, the first region, and the second region, refer to the description herein.

[0286] According to the embodiments, the first region and the second region may independently include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), cobalt (Co), copper (Cu), or any combination thereof.

[0287] According to another embodiment, the first region may include titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), or any combination thereof, and the second region may include tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

[0288] According to another embodiment, the first region may include a metal nitride, a metal oxynitride, or any combination thereof, and the second region may include a conductive metal.

[0289] According to another embodiment, the first region may include titanium nitride, titanium oxynitride, or any combination thereof, and the titanium nitride and titanium oxynitride may each optionally further include indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

[0290] Figure 1A and Figure 2 This is a diagram illustrating an embodiment of a metal-containing membrane treatment method.

[0291] Reference Figure 1A A substrate 10 is provided having a metal-containing film 20A. Although in Figure 1A Although not shown, various circuit elements may optionally be additionally disposed between the substrate 10 and the metal-containing film 20A.

[0292] The metal-containing film 20A may include a first region 21 and a second region 22. The first region 21 and the second region 22 may be disposed separately from each other or may be disposed at least partially in contact with each other, and the metal-containing film 20A may have various patterns. The metal-containing film 20A including the first region 21 and the second region 22 may contact the composition 30, thereby removing a portion of the metal-containing film 20A. For example, the metal-containing film 20A may contact the composition 30 during etching, cleaning, and / or polishing processes. The composition 30 may include oxidants, phosphoric acid, organic acids, and etching control agents as described herein, and for a detailed description thereof, refer to the description herein.

[0293] The etching rate ratio obtained by dividing the first etching rate of the composition 30 etching the first region 21 by the second etching rate of the composition 30 etching the second region 22 can be 0.04 or greater. For example, the etching rate ratio obtained by dividing the first etching rate of the composition 30 etching the first region 21 by the second etching rate of the composition 30 etching the second region 22 may be about 0.05 or greater, about 0.06 or greater, about 0.04 to about 1.0, about 0.05 to about 1.0, about 0.06 to about 1.0, about 0.04 to about 0.5, about 0.05 to about 0.5, about 0.06 to about 0.5, about 0.04 to about 0.3, about 0.05 to about 0.3, about 0.06 to about 0.3, about 0.04 to about 0.2, about 0.05 to about 0.2, about 0.06 to about 0.2, about 0.04 to about 0.15, about 0.05 to about 0.15, about 0.06 to about 0.15, or about 0.06 to about 0.13.

[0294] Figure 1BThis is a schematic diagram illustrating the surface of the metal-containing film 20A that can contact the composition 30. The etched area ratio, obtained by dividing the first area of ​​the first region 21 exposed to contact the composition 30 by the second area of ​​the second region 22 exposed to contact the composition 30, can be about 0.05 to about 1.0, about 0.05 to about 0.9, about 0.05 to about 0.7, about 0.05 to about 0.5, about 0.05 to about 0.4, about 0.05 to about 0.3, or about 0.05 to about 0.2.

[0295] When the metal-containing film 20A comes into contact with the composition 30, the high reactivity of the metal contained in the metal-containing film 20A (e.g., the metal such as molybdenum contained in the second region 22) can be controlled through the interaction of the oxidant, phosphoric acid, organic acid, and etching control agent included in the composition 30. As a result, the etching rate (e.g., the etching rate of the second region 22) in the regions containing relatively highly reactive metals in the first region 21 and the second region 22 can be appropriately controlled. Therefore, portions of both the first region 21 and the second region 22 can be etched, allowing the formation of... Figure 2 The metal-containing film pattern 20 shown has a substantially flat surface (e.g., a small step height difference or no step height difference between the first region 21 and the second region 22). Furthermore, after the contact process with the composition 30, various byproducts originating from the metal-containing film 20A (e.g., metal oxides such as molybdenum oxide originating from the metal-containing film 20A) are substantially absent from the surface of the metal-containing film pattern 20. The presence or absence of byproducts can be verified, for example, by analysis such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), etc.

[0296] Figure 3 and 4 This is a diagram illustrating another embodiment of a metal-containing membrane treatment method.

[0297] refer to Figure 3 A substrate 10 is provided, wherein, in addition to the metal-containing film 20A, an additional material 40 is disposed adjacent to the metal-containing film 20A. For Figure 3 For a description of the metal-containing film 20A and the substrate 10, please refer to [reference needed]. Figure 1A .

[0298] Figure 3 The additional material 40 may be disposed spaced apart from the metal-containing membrane 20A, or may be at least partially in contact with it. As used herein, the term "additional material 40" refers to a material different from the metal-containing membrane 20A, which is disposed adjacent to the metal-containing membrane 20A and located in an area that may be affected by the composition 30 during the treatment of the metal-containing membrane 20A using the composition 30.

[0299] The additional material 40 may include at least one of an insulating material and a semiconductor material. The insulating material and the semiconductor material may include a variety of known materials.

[0300] Insulating materials may include various oxides, nitrides, oxynitrides, high-dielectric materials, or combinations thereof. For example, insulating materials may include silicon oxides, silicon nitrides, silicon oxynitrides, aluminum oxides, hafnium oxides, hafnium oxynitrides, zirconium oxides, or combinations thereof. Hafnium oxides and hafnium oxynitrides may optionally further include Si, Ta, Ti, Zr, or any combination thereof. As another example, insulating materials may include tetraethyl orthosilicate (TEOS), hydrogen silsesquioxane (HSQ), methyl silsesquioxane (MSQ), etc.

[0301] Semiconductor materials may be, for example, materials included in channels, and may include: group IV semiconductor materials such as silicon, germanium (Ge), silicon-germanium (SiGe), and silicon carbide (SiC); group III-V semiconductor materials such as gallium arsenide (GaAs), indium arsenide (InAs), and indium phosphide (InP); and oxide semiconductors, nitride semiconductors, and oxynitride semiconductors. Oxide semiconductors may include, for example, indium gallium zinc oxide (IGZO), indium tin zinc oxide (ITZO), indium tin gallium oxide (ITGO), indium tungsten oxide (IWO), indium tin oxide (ITO), ZnO, Cu2O, or any combination thereof.

[0302] like Figure 3 As shown, a metal-containing film 20A, including a first region 21 and a second region 22, and additional material 40 can be contacted with the composition 30, and a portion of the metal-containing film 20A can be removed. For example, the metal-containing film 20A can be contacted with the composition 30 during etching, cleaning, and / or polishing processes of the metal-containing film 20A, including the first region 21 and the second region 22. The composition 30 includes an oxidant, phosphoric acid, an organic acid, and an etching control agent as described herein, and for a detailed description thereof, refer to the description herein.

[0303] When the metal-containing film 20A comes into contact with the composition 30, a portion of the metal-containing film 20A can be removed. Specifically, during contact between the metal-containing film 20A and the composition 30, the high reactivity of the metal included in the metal-containing film 20A (e.g., the metal such as molybdenum included in the second region 22) can be controlled due to the interaction between the oxidant, phosphoric acid, organic acid, and etching control agent included in the composition 30. As a result, the etching rate (e.g., the etching rate of the second region 22) of the regions in the first region 21 and the second region 22 containing relatively highly reactive metals can be appropriately controlled, such that portions of both the first region 21 and the second region 22 are etched. Therefore, as Figure 4As shown, a metal-containing film pattern 20 with a substantially flat surface (e.g., a small step height difference or no step height difference between the first region 21 and the second region 22) can be formed. Furthermore, after the contact process with the composition 30, various byproducts originating from the metal-containing film 20A (e.g., metal oxides such as molybdenum oxide originating from the metal-containing film 20A) remain substantially absent from the surface of the metal-containing film pattern 20. Additionally, an additional material 40, including, for example, at least one insulating material and a semiconductor material, remains substantially undamaged by the composition 30.

[0304] Methods for manufacturing electronic devices

[0305] Using the above-described composition, high-quality electronic devices can be manufactured. Therefore, a method for manufacturing electronic devices using the described composition can be provided.

[0306] According to one aspect of this disclosure,

[0307] Provides a method for manufacturing electronic devices including transistors.

[0308] The transistor includes,

[0309] Ditch;

[0310] The source and drain electrodes are spaced apart from each other and electrically connected to the channel;

[0311] Gate electrode; and

[0312] A gate insulating film disposed between the gate electrode and the channel.

[0313] The method includes:

[0314] Provides a barrier layer including metal nitrides, metal oxynitrides, or combinations thereof;

[0315] Provides a conductive layer comprising a conductive metal; and

[0316] The gate electrode is formed by contacting the barrier layer and the conductive layer with the composition to etch a portion of the barrier layer and a portion of the conductive layer.

[0317] According to one aspect of this disclosure, a method of manufacturing an electronic device may include: forming a structure comprising source and drain electrodes spaced apart from each other and electrically connected to a channel; and providing a gate electrode and a gate insulating film on the structure, wherein the gate insulating film is between the gate electrode and the channel. The gate electrode may be provided by: providing a barrier layer comprising a metal nitride, a metal oxynitride, or any combination thereof; providing a conductive layer comprising a conductive metal; and forming the gate electrode by contacting the barrier layer and the conductive layer with the composition to etch a portion of the barrier layer and a portion of the conductive layer.

[0318] The channel may include, for example, semiconductor materials as described herein. For example, the channel may include: group IV semiconductor materials such as silicon, germanium (Ge), silicon-germanium (SiGe), and silicon carbide (SiC); group III-V semiconductor materials such as gallium arsenide (GaAs), indium arsenide (InAs), and indium phosphide (InP); oxide semiconductors, nitride semiconductors, and oxynitride semiconductors. Oxide semiconductors may include, for example, indium gallium zinc oxide (IGZO), indium tin zinc oxide (ITZO), indium tin gallium oxide (ITGO), indium tungsten oxide (IWO), indium tin oxide (ITO), ZnO, Cu2O, or any combination thereof.

[0319] The gate insulating film may include an insulating material capable of electrically insulating the gate electrode from the channel. For example, the gate insulating film may include various oxides, nitrides, oxynitrides, high-k materials, or combinations thereof. For example, the gate insulating film may include silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, hafnium oxide, hafnium oxynitride, zirconium oxide, or combinations thereof. Hafnium oxide and hafnium oxynitride may optionally further include Si, Ta, Ti, Zr, or any combination thereof.

[0320] The gate electrode may include a barrier layer and a conductive layer. The barrier layer may be disposed, for example, between a gate insulating film and a conductive layer.

[0321] To provide a gate electrode, a barrier layer and a conductive layer may be provided. For example, after forming the barrier layer, a conductive layer may be formed on the surface of the barrier layer. However, depending on the structure of the channel and / or the gate electrode, various modifications are possible, such as forming a barrier layer on the surface of the conductive layer after forming the conductive layer.

[0322] A barrier layer may be provided to limit and / or prevent the peripheral (peripheral) diffusion of conductive metals (e.g., metal ions) included in the conductive layer and / or promote the smooth deposition of the conductive layer.

[0323] For a detailed description of each of the metal nitrides and / or metal oxynitrides that may be contained in the barrier layer, please refer to the description of each of the metal nitrides and / or metal oxynitrides that may be contained in the first region of the metal-containing film herein.

[0324] According to an embodiment, the barrier layer may include titanium nitride, titanium oxynitride, or a combination thereof, and each of the titanium nitride and titanium oxynitride may optionally further include indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

[0325] For a detailed description of conductive metals that may be included in the conductive layer, refer to the description herein of conductive metals that may be included in the second region of the metal-containing film.

[0326] According to an embodiment, the conductive layer may include tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

[0327] Subsequently, the barrier layer and the conductive layer can be contacted with the composition described herein to etch a portion of the barrier layer and a portion of the conductive layer, thereby forming a gate electrode.

[0328] When the barrier layer and conductive layer are contacted with the composition as described herein, the high reactivity of the conductive metal included in the conductive layer can be controlled by the interaction between the oxidant, phosphoric acid, organic acid, and etch control agent in the composition. As a result, the etch rate of the conductive layer can be appropriately controlled, allowing portions of both the barrier layer and the conductive layer to be etched. Therefore, a gate electrode with a substantially flat surface (e.g., a small step height difference or no step height difference between the barrier layer and the conductive layer) can be formed. Furthermore, after the contact process with the composition, the surface of the gate electrode can be substantially free of various byproducts originating from the conductive layer (e.g., oxides of the conductive metal). Moreover, since at least one of the channels and gate insulating film disposed adjacent to the gate electrode can be substantially undamaged by the composition, high-quality electronic devices including gate electrodes with precise patterns can be manufactured without damaging the areas adjacent to the gate electrode.

[0329] Electronic devices can be semiconductor memory devices.

[0330] For example, electronic devices may include volatile memory devices such as dynamic random access memory (“DRAM”) devices or static random access memory (“SRAM”) devices, resistive random access memory (“ReRAM”) devices, electrically erasable programmable read-only memory (“EEPROM”) devices, flash memory (which may also be considered a subset of EEPROM) devices, ferroelectric random access memory (“FRAM”) devices, magnetoresistive random access memory (“MRAM”) devices, and non-volatile memory devices such as other semiconductor devices capable of storing information.

[0331] According to the implementation method, the electronic device may be a DRAM device.

[0332] In the following text, reference will be made to Figure 5 , 6A Sections 6B, 7, 8, and 9 describe the manufacturing methods of electronic devices in more detail.

[0333] Figure 5 Figure 6 is a schematic plan view of the electronic device 3000 according to the embodiment, and Figure 6 is... Figure 5 A perspective view of the electronic device 3000 shown. Figure 5 The electronic device 3000 can be a DRAM device.

[0334] Reference Figure 5 , 6A And 6B, the electronic device 3000 includes a plurality of unit elements 3100 arranged in an array. Each unit element 3100 has a 1T1C structure including a transistor and a capacitor (or consisting of a transistor and a capacitor).

[0335] Electronic device 3000 includes a transistor structure 100 and a plurality of capacitors 3500 provided to the transistor structure 100. The transistor structure 100 may be, for example, a vertical channel array transistor structure including channels arranged perpendicularly to a substrate (see [link to documentation]). Figure 6A ), or a channel array transistor structure comprising channels arranged and stacked horizontally relative to the substrate (see Figure 6B ).

[0336] In the transistor structure 100, a plurality of gate electrodes (or word lines) 150 and a plurality of bit lines 160 are provided to intersect each other. Each gate electrode 150 is provided to extend in a first direction (e.g., the x-axis direction), and each bit line 160 is provided to extend in a second direction (e.g., the y-axis direction) intersecting the first direction. The transistor is arranged at the points where the plurality of gate electrodes 150 and the plurality of bit lines 160 intersect.

[0337] Figures 7 to 9 It is an illustrative explanation Figure 6A A partial diagram of the manufacturing process of the transistor structure 100 shown.

[0338] exist Figure 7 In the transistor structure 100, there are a substrate 110 and a plurality of channels 140 arranged in an array on the substrate 110. The plurality of channels 140 may be arranged in a two-dimensional array on a plane (e.g., the xy plane) of the substrate 110.

[0339] Substrate 110 may include a semiconductor, such as silicon (Si). As a specific example, substrate 110 may be a silicon substrate doped with n-type impurities. However, this is merely illustrative. Alternatively, substrate 110 may include, for example, group IV semiconductor materials such as germanium (Ge), silicon germanium (SiGe), or silicon carbide (SiC); group III-V semiconductor materials such as gallium arsenide (GaAs), indium arsenide (InAs), or indium phosphide (InP); or oxide semiconductors, nitride semiconductors, oxynitride semiconductors, etc.

[0340] Multiple channels 140 may each be provided to extend vertically from the substrate 110. Each channel 140 may be provided to project vertically from the upper surface of the substrate 110. Each channel 140 may be integrally formed with the substrate 110 and may therefore include the same semiconductor material as the semiconductor substrate 110. Figure 7 In this diagram, the channel 140 is shown to be integrally formed with the substrate 110, but various modifications are possible, such as the channel 140 being formed separately from the substrate 110.

[0341] A source S and a drain D are provided at the bottom and top of each channel 140, respectively. The source S is provided to be electrically connected to the bottom of the channel 140, and the drain D is provided to be connected to the top of the channel 140. For example, the source S and drain D can be formed by forming doped regions. Figure 5 The capacitor 3500 shown can be connected to the drain D provided at the upper portion of the channel 140.

[0342] On the top surface of substrate 110, sources S are provided in an array corresponding to channels 140. Below the sources S, a plurality of bit lines 160 are provided extending along a second direction (e.g., the y-axis direction). Each bit line 160 is electrically connected to the sources S arranged along the second direction. The plurality of bit lines 160 may be formed in substrate 110 and therefore may comprise the same semiconductor material as substrate 110. Figure 7 In the middle, bit line 160 is formed using a material separate from substrate 110; however, various modifications are possible.

[0343] Multiple insulating materials 170 may be provided in the substrate 110 between bit lines 160. The multiple insulating materials 170 may be provided to extend along a second direction parallel to the multiple bit lines 160, thereby separating the multiple bit lines 160 in the substrate 110. The insulating materials 170 may include, for example, silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, hafnium oxide, hafnium oxynitride, zirconium oxide, or combinations thereof.

[0344] A gate insulating film 130 is provided on the surface of the channel 140. The gate insulating film 130 may include insulating materials as described herein, such as silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, hafnium oxide, hafnium oxynitride, zirconium oxide, or combinations thereof.

[0345] In the substrate 110 provided with a channel 140 and a gate insulating film 130 as described above, a barrier layer 151 comprising a metal nitride, a metal oxynitride, or a combination thereof, and a conductive layer 152 comprising a conductive metal are provided in the trench at least partially defined by the gate insulating film 130, such as Figure 7 As shown in the diagram. For example, after forming the barrier layer 151, a conductive layer 152 may be formed on the surface of the barrier layer 151. However, depending on the structure of the channel 140 and / or the gate electrode 150, various modifications are possible, such as forming the barrier layer 151 on the surface of the conductive layer 152 after forming the conductive layer 152. For a description of the metal nitrides and / or metal oxynitrides included in the barrier layer 151 and the conductive metals included in the conductive layer 152, refer to the description herein.

[0346] Subsequently, as Figure 7 As shown, an embedded insulating layer 180 is provided in a trench at least partially defined by a conductive layer 152. The embedded insulating layer 180 can be used for protection. Figure 8 The gate electrode 150 is protected from the penetration of oxygen and other substances. After the embedded insulating layer 180 is formed, a planarization process can be performed to expose the top surfaces of the barrier layer 151 and the conductive layer 152.

[0347] Then, the remaining top surfaces of the barrier layer 151 and the conductive layer 152 are brought into contact with the composition 30 to etch a portion of the barrier layer 151 and a portion of the conductive layer 152, thereby forming a composition having Figure 8 The gate electrode 150 of the pattern shown. Figure 7 The composition 30 includes an oxidant, phosphoric acid, organic acid, and etching control agent as described in this specification, and for a detailed description thereof, refer to the description herein.

[0348] The etching rate ratio obtained by dividing the first etching rate of the composition 30 etching the barrier layer 151 by the second etching rate of the composition 30 etching the conductive layer 152 can be 0.04 or greater. For example, the etching rate ratio obtained by dividing the first etching rate of the composition 30 etching the barrier layer 151 by the second etching rate of the composition 30 etching the conductive layer 152 may be 0.05 or greater, about 0.06 or greater, about 0.04 to about 1.0, about 0.05 to about 1.0, about 0.06 to about 1.0, about 0.04 to about 0.5, about 0.05 to about 0.5, about 0.06 to about 0.5, about 0.04 to about 0.3, about 0.05 to about 0.3, about 0.06 to about 0.3, about 0.04 to about 0.2, about 0.05 to about 0.2, about 0.06 to about 0.2, about 0.04 to about 0.15, about 0.05 to about 0.15, about 0.06 to about 0.15, or about 0.06 to about 0.13.

[0349] Meanwhile, the etch area ratio obtained by dividing the first area of ​​the barrier layer 151 exposed to contact with the composition 30 by the second area of ​​the conductive layer 152 exposed to contact with the composition 30 can be about 0.05 to about 1.0, about 0.05 to about 0.9, about 0.05 to about 0.7, about 0.05 to about 0.5, about 0.05 to about 0.4, about 0.05 to about 0.3, or about 0.05 to about 0.2.

[0350] When the barrier layer 151 and the conductive layer 152 come into contact with the composition 30, the high reactivity of the conductive metal included in the conductive layer 152 can be controlled through the interaction between the oxidant, phosphoric acid, organic acid, and etching control agent contained in the composition 30. As a result, the etching rate of the conductive layer 152 can be appropriately controlled, and portions of both the barrier layer 151 and the conductive layer 152 can be etched. Therefore, as... Figure 8 As shown, a gate electrode 150 with a substantially flat top surface (e.g., a small step height difference or no step height difference between the barrier layer 151 and the conductive layer 152) can be formed. Furthermore, after the contact process with the composition 30, the surface of the gate electrode 150 can be substantially free of various byproducts originating from the conductive layer 152 (e.g., oxides of conductive metals). Moreover, the channel 140, gate insulating film 130, and embedded insulating layer 180 arranged adjacent to the gate electrode 150 can be substantially undamaged by the composition 30, enabling the manufacture of a high-quality electronic device 3000 with a precisely patterned gate electrode 150 without damaging the areas adjacent to the gate electrode 150, such as the channel 140, gate insulating film 130, and embedded insulating layer 180.

[0351] exist Figure 8 In this configuration, a plurality of gate electrodes 150 on the substrate 110 may be arranged to extend along a first direction (e.g., the x-axis direction). The first direction may be a direction intersecting the second direction described above. For example, the first direction may be a direction perpendicular to the second direction. However, it is not limited to this.

[0352] Each gate electrode 150 is provided to correspond to a channel 140 arranged along a first direction. Specifically, each gate electrode 150 is provided to surround a channel 140 arranged along the first direction. These gate electrodes 150 can function as word lines.

[0353] Multiple gate electrodes 150 may be provided to intersect with multiple insulating materials 170 provided below them. The top surface of the insulating material 170 may be provided to be adjacent to the bottom surface of the gate electrode 150. The top of the insulating material 170 may be provided to protrude from the bottom of the gate electrode 150, but is not limited thereto.

[0354] Subsequently, as Figure 9As shown, an insulating layer 190 may be additionally provided on the surface of the etched barrier layer 151 and the surface of the etched conductive layer 152. The insulating layer 190 may be used to further insulate the gate electrode 150 from the channel 140 and may include, for example, an insulating material as described herein.

[0355] Methods of manufacturing electronic devices

[0356] Reference Figure 10 An embodiment of a method for manufacturing an electronic device may include: preparing a substrate S100 on which a metal-containing film is provided; contacting the metal-containing film with a composition as described herein S110; and manufacturing electronic components using one or more subsequent processes S120. Subsequent processes may include various known processes for manufacturing electronic components, such as capacitor forming processes.

[0357] Example 1 and Comparative Examples C1, C2 and C21

[0358] The oxidizing agents, inorganic acids, organic acids, and etching control agents listed in Table 1 are mixed in the amounts described in Table 1 to produce the compositions of Example 1 and Comparative Examples C1, C2, and C21. The remaining portions of each composition may correspond to water (deionized water).

[0359] Evaluation Example 1

[0360] The composition of Example 1 was placed in three separate beakers and heated to 60°C. Samples of titanium nitride, molybdenum, and silicon oxide films, each with a size of 1 cm × 1 cm, were then immersed in each beaker for 1 minute. The thicknesses of the titanium nitride, molybdenum, and silicon oxide films were then measured using an ellipsometer (M-2000, JAWoolam), a four-point resistance meter, and X-ray fluorescence spectroscopy (XRF) to evaluate the etching rates of the titanium nitride film (also known as the "titanium nitride film etching rate"), the molybdenum film (also known as the "molybdenum film etching rate"), the etching rate ratio R obtained by dividing the titanium nitride film etching rate by the molybdenum film etching rate, and the silicon oxide film (also known as the "silicon oxide film etching rate"). The results, along with the pH of Example 1, are summarized in Table 1. The unit for each etching rate is "Å / min".

[0361] The compositions of comparative examples C1 and C2 were tested repeatedly, and the results are summarized in Table 1.

[0362] In addition, for the composition of Comparative Example C21, in order to evaluate it in the same manner as in Evaluation Example 1, the composition of Comparative Example C21 was placed in a beaker and heated to 60°C. However, brown gas was generated in the beaker during heating, and therefore, the etching rate of the titanium nitride film of Comparative Example C21, the etching rate of the molybdenum film of Comparative Example C21, and the etching rate of the silicon oxide film of Comparative Example C21 could not be evaluated.

[0363] In Tables 1 to 5, "-" indicates "no evaluation value". In particular, in Tables 1 to 5, an etching rate indicated by "-" means that the etching rate is so small as to be unmeasurable, and therefore, almost no etching occurs.

[0364] [Table 1]

[0365]

[0366]

[0367] As can be confirmed from Table 1, i) the composition of Comparative Example C1, which does not include an oxidant, substantially does not etch the titanium nitride-containing film and the molybdenum film, and ii) the composition of Comparative Example C2, which includes HF (hydrofluoric acid) as an oxidant, substantially does not etch the titanium nitride-containing film and the molybdenum film, but also damages the silicon oxide film. On the other hand, it can be confirmed that the composition of Example 1 can more appropriately etch both the titanium nitride-containing film and the molybdenum film simultaneously without substantially damaging the silicon oxide film, and is therefore useful for more uniform etching of metal-containing films with multiple compositions.

[0368] Meanwhile, it can be confirmed that the composition of Comparative Example C21 does not have sufficient stability for effective treatment of metal-containing films with multiple compositions.

[0369] Comparative examples C3 to C5 and C31

[0370] The oxidizing agents, inorganic acids, organic acids, and etching control agents listed in Table 2 were mixed in the amounts described in Table 2 to produce the compositions of Comparative Examples C3 to C5 and C31. The remainder of each composition corresponds to water (deionized water).

[0371] Evaluation Example 2

[0372] For the composition of Comparative Example C3, pH, molybdenum film etching rate, and silicon oxide film etching rate were evaluated according to the method described in Evaluation Example 1, and the results are summarized in Table 2. For comparison, the pH, molybdenum film etching rate, and silicon oxide film etching rate of the composition of Example 1 are also shown in Table 2.

[0373] The composition of Comparative Example C31 was tested repeatedly, and the results are summarized in Table 2.

[0374] Meanwhile, for the compositions of Comparative Examples C4 and C5, in order to evaluate them in the same manner as in Evaluation Example 1, the compositions of Comparative Examples C4 and C5 were each placed in a beaker and heated to 60°C. However, gas was generated in the beaker during heating, and therefore, the etching rates of the molybdenum film and the silicon oxide film of Comparative Examples C4 and C5 could not be evaluated.

[0375] [Table 2]

[0376]

[0377] As can be confirmed from Table 2, the molybdenum film etching rate of the compositions of Comparative Examples C3 and C31, excluding phosphoric acid, is greater than that of the molybdenum film etching rate of the composition of Example 1. Therefore, it can be confirmed that, compared to the compositions of Comparative Examples C3 and C31, the composition of Example 1 can etch the molybdenum film at a more appropriate etching rate without substantially damaging the silicon oxide film, and is thus useful for more uniform etching of metal-containing films with various compositions.

[0378] Meanwhile, it can be confirmed that the compositions of comparative examples C4 and C5 do not have sufficient stability for effectively treating metal-containing films with multiple compositions.

[0379] Comparative example C6

[0380] The oxidizing agents, inorganic acids, organic acids, and etching control agents listed in Table 3 were mixed in the amounts described in Table 3 to prepare the composition of Comparative Example C6. The remainder of the composition corresponds to water (deionized water).

[0381] Evaluation Example 3

[0382] For the composition of Comparative Example C6, pH, molybdenum film etching rate, and silicon oxide film etching rate were evaluated according to the method described in Evaluation Example 1, and the results are summarized in Table 3. For comparison, the pH, molybdenum film etching rate, and silicon oxide film etching rate of the composition of Example 1 are also shown in Table 3.

[0383] [Table 3]

[0384]

[0385] As can be confirmed from Table 3, the molybdenum film etching rate of the composition of Comparative Example C6, which does not contain acetic acid, is greater than that of the molybdenum film etching rate of the composition of Example 1. Therefore, it can be confirmed that the composition of Example 1 can etch molybdenum films at a more appropriate etching rate compared to the composition of Comparative Example C6, and is thus useful for more uniform etching of metal-containing films with various compositions.

[0386] Comparative Examples C7 to C12

[0387] The oxidizing agents, inorganic acids, organic acids, and etching control agents listed in Table 4 are mixed in the amounts described in Table 4 to produce the compositions of Comparative Examples C7 to C12. The remainder of each composition corresponds to water (deionized water).

[0388] Evaluation Example 4

[0389] For each composition in Comparative Examples C7 to C12, pH, molybdenum film etching rate, and silicon oxide film etching rate were evaluated according to the method described in Evaluation Example 1, and the results are summarized in Table 4. For comparison, the pH, molybdenum film etching rate, and silicon oxide film etching rate of the compositions of Example 1 are also shown in Table 4.

[0390] [Table 4]

[0391]

[0392]

[0393]

[0394]

[0395] As can be confirmed from Table 4, the molybdenum film etching rates of the composition excluding the etching control agent in Comparative Example C7, the compositions including hydroxyl-containing and nitrogen-containing compounds as etching control agents in Comparative Examples C8 to C11, and the compositions including nitrogen-free compounds as etching control agents in Comparative Example C12 are all greater than the molybdenum film etching rate of the composition of Example 1. Therefore, it can be confirmed that, compared to the compositions of Comparative Examples C7 to C12, the composition of Example 1 can etch the molybdenum film at a more appropriate etching rate, and is therefore useful for more uniform etching of metal-containing films having various compositions.

[0396] Examples 2 to 4

[0397] The compositions of Examples 2 to 4 were prepared by mixing the oxidizing agents, inorganic acids, organic acids, and etching control agents listed in Table 5 in the amounts described in Table 5. The remainder of each composition corresponds to water (deionized water).

[0398] Evaluation Example 5

[0399] For each composition of Examples 2 to 4, pH, etching rate of the titanium nitride film, etching rate of the molybdenum film, R, and etching rate of the silicon oxide film were evaluated according to the method described in Evaluation Example 1, and the results are summarized in Table 5. The pH, etching rate of the titanium nitride film, etching rate of the molybdenum film, R, and etching rate of the silicon oxide film of the composition of Example 1 are also shown in Table 5.

[0400] [Table 5]

[0401]

[0402]

[0403] As can be confirmed from Table 5, the compositions of Examples 2 to 4 can simultaneously etch both the titanium nitride film and the molybdenum film at a more appropriate etching ratio, without substantially damaging the silicon oxide film, which is comparable to the composition of Example 1, and therefore can be usefully used for more uniform etching of metal-containing films with multiple compositions.

[0404] Example 5 and Comparative Example C41

[0405] The oxidizing agents, inorganic acids, organic acids, and etching control agents listed in Table 6 were mixed in the amounts described in Table 6 to prepare the compositions of Example 5 and Comparative Example C41. The remainder of each composition corresponds to water (deionized water). In Comparative Example C41, the polyethyleneimine (PEI) used as the etching control agent has a weight-average molecular weight of 800 g / mol (n is an integer satisfying the weight-average molecular weight), and the amounts of PEI in Table 6 represent the amounts of the solid component of PEI.

[0406] Evaluation Example 6

[0407] The compositions of Example 5 and Comparative Example C41 were placed in two separate beakers and heated to 60°C. Then, 1H NMR analysis was performed on the compositions in each beaker to evaluate whether the structures of compounds A1 and PEI changed after mixing with a high concentration (70 wt%) of phosphoric acid and heating at a high temperature (60°C). The results are summarized in Table 6. Furthermore, the 1H NMR data of compound A1 after mixing with a high concentration (70 wt%) of phosphoric acid and heating at a high temperature (60°C) are shown below. Figure 11A The 1H NMR data of PEI after mixing with high concentration (70 wt%) phosphoric acid and heating at high temperature (60 °C) are shown in the figure. Figure 11B middle.

[0408] Table 6

[0409]

[0410] X: In 1H NMR, almost no peaks were observed corresponding to amine oxides (amine oxides) and / or amides, which are structural alteration products of amine-containing etching control agents.

[0411] O: In 1H NMR, many peaks were observed corresponding to amine oxides (amine oxides) and / or amides, which are structural modification products of amine-containing etching control agents.

[0412]

[0413]

[0414] From Figure 6, Figure 11A and Figure 11B It was confirmed that the structure of compound A1 remained essentially unchanged after mixing with high-concentration (70 wt%) phosphoric acid and heating at high temperature (60 °C), but the structure of PEI changed after mixing with high-concentration (70 wt%) phosphoric acid and heating at high temperature (60 °C). Therefore, it is confirmed that compound A1 is stable even under the condition of mixing with high-concentration (70 wt%) phosphoric acid and heating at high temperature (60 °C), but PEI is not stable under the same conditions.

[0415] Evaluation Example 7

[0416] Prepare two samples 1 cm × 1 cm, each with two silicon oxide films (refer to...). Figure 12 A molybdenum film (refer to) arranged between regions “S1” and “S2” in the diagram. Figure 12 The “M” region in the text) and films containing titanium nitrides (see reference) Figure 12 (The "T" area in the text). Figure 12 This is a transmission electron microscope (TEM) image of sample 1.

[0417] Subsequently, the compositions of Example 1 (using hydrogen peroxide as an oxidant) and Comparative Example C2 (using HF as an oxidant) were placed in two separate beakers and heated to 60°C. Sample 1 was then immersed in each beaker for 10 minutes, rinsed with deionized water, and dried to obtain Sample 1 immersed in each of the compositions. TEM images of Sample 1 immersed in the composition of Example 1 are shown below. Figure 13A In the middle, TEM images of sample 1 immersed in the composition of comparative example C2 are shown. Figure 13B middle.

[0418] It can be confirmed that the TEM image of sample 1, which is shown immersed in the composition of Example 1, is included. Figure 13A In the study, regions “S1” and “S2” were observed as two silicon oxide films, but a TEM image of sample 1 immersed in the composition of comparative example C2 is shown within them. Figure 13B In the study, the “S1” region on the left, which is a silicon oxide film, was not observed, and the significant amount of the “S2” region on the right, which is also a silicon oxide film, was also lost.

[0419] It can be confirmed that, unlike the composition of Comparative Example C2, the composition of Example 1 can be usefully used to process a variety of metal-containing films without substantially damaging the silicon oxide film adjacent to the metal-containing film.

[0420] Because the etching rate is easier to control for various metal-containing films, the composition can be used more effectively in a variety of processing techniques for metal-containing films, such as etching, cleaning, and polishing. Therefore, by using the composition to process metal-containing films, higher quality electronic and semiconductor devices can be manufactured.

[0421] It should be understood that the embodiments described herein are to be considered in a descriptive sense only and are not intended for limiting purposes. The descriptions of features or aspects within each embodiment should typically be considered applicable to other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the accompanying drawings, those skilled in the art will understand that various changes in form and detail may be made therein without departing from the spirit and scope defined by the appended claims.

Claims

1. A composition comprising: an oxidizing agent; a phosphoric acid; an organic acid; and an etch control agent, wherein the oxidizing agent comprises hydrogen peroxide, an iodine-containing compound, or any combination thereof, wherein the etch control agent comprises a hydroxyl-free and nitrogen-containing compound, wherein the hydroxyl-free and nitrogen-containing compound comprises a compound represented by Formula 5, a compound represented by Formula 6, or any combination thereof, and wherein the composition has a pH of 2 or less, Formula 5 T 52 -[(L5) a5 ]-T 51 Formula 6 CY6-[L6-N(R 61 )(R 62 )] a6 In Equation 5, L5 is *-C(Z) 51 (Z) 52 )-*'、*-N(Z 53 )-*', or *-C(=O)-*', in Formula 5, a5 is an integer from 2 to 30, In formula 5, T 51 is *-N(R 51 )(R 52 ), and T 52 is *-N(R 53 )(R 54 ), in Formula 6, ring CY6 is a saturated or unsaturated carbocyclic group having 5 to 15 carbon atoms, a saturated heterocyclic group having 2 to 15 carbon atoms, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a carbazole group, a dibenzofuran group, or a dibenzothiophene group, In Formula 6, L6is a single bond or C1-C 30 alkylene, in Formula 6, a6 is an integer from 1 to 5, In formulae 5 and 6, Z 51 , Z 52 , Z 53 , R 51 , R 52 , R 53 , R 54 , R 61 , and R 62 are each independently: hydrogen or an amino group; or Unsubstituted or amino- or mono(C1-C) 30 alkyl)amino, di(C1-C) 30 Alkyl)amino, *-C(=O)-N(Q) 51 (Q) 52 C1-C replaced by, or any combination thereof 30 alkyl, Q 51 and Q 52 each independently is: hydrogen; or Unsubstituted or amino- or mono(C1-C) 30 alkyl)amino, di(C1-C) 30 alkyl)amino, or any combination thereof substituted C1-C 30 Alkyl groups, and * and *' each represent a binding site to an adjacent atom.

2. The composition of claim 1, wherein the amount of the oxidizing agent is about 0.001 wt% to about 3 wt% based on 100 wt% of the composition.

3. The composition of claim 1, wherein the amount of the phosphoric acid is about 10 wt% to about 85 wt% based on 100 wt% of the composition.

4. The composition of claim 1, wherein the organic acid comprises a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, or any combination thereof.

5. The composition of claim 1, wherein the organic acid comprises formic acid, acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, gallic acid, succinic acid, malic acid, maleic acid, crotonic acid, fumaric acid, ascorbic acid, glutamic acid, citric acid, tartaric acid, glycolic acid, lactic acid, benzoic acid, salicylic acid, or any combination thereof.

6. The composition of claim 1, wherein the amount of the organic acid is about 0.1 wt% to about 15 wt% based on 100 wt% of the composition.

7. The composition of claim 1, wherein, In formula 5, i) each L5is *-C(Z 51 )(Z 52 )-* and a5is an integer from 2 to 11, or ii) each L5is *-C(Z 51 )(Z 52 )-* or *-N(Z 53 )-* and a5is an integer from 5 to 11, and in Formula 6, ring CY6 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 phenyl group, a naphthalene group, a piperazine group, a pyrrolidine group, a piperidine group, an azepane group, a tetrahydrofuran group, a tetrahydrothiophene group, a tetrahydro-2H-pyran group, a tetrahydro-2H-thiopyran group, a 4H-pyran-4-one group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a carbazole group, a dibenzofuran group, or a dibenzothiophene group.

8. The composition of claim 1, wherein the amount of the etch control agent is about 0.01 wt% to about 5 wt% based on 100 wt% of the composition.

9. The composition of claim 1, wherein the composition has a pH of about -3.0 to about 1.

0.

10. A method of processing a metal-containing film, comprising: preparing a substrate comprising the metal-containing film, the metal-containing film comprising a first region and a second region; and contacting the metal-containing film with a composition according to any one of claims 1 to 9; wherein the first region and the second region independently comprise titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), cobalt (Co), copper (Cu), or any combination thereof, wherein the material comprised in the first region is different from the material comprised in the second region.

11. The method of claim 10, wherein the first region comprises titanium (Ti), indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), or any combination thereof, and the second region comprises tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

12. The method of claim 10, wherein the first region comprises a metal nitride, a metal oxynitride, or any combination thereof, and the second region comprises an electrically conductive metal.

13. The method of claim 10, wherein the first region comprises titanium nitride, titanium oxynitride, or any combination thereof, and each of the titanium nitride and the titanium oxynitride optionally further comprises indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof.

14. The method of claim 10, wherein an etch area ratio is in a range from about 0.05 to about 1.0, the etch area ratio being a ratio obtained by dividing a first area of the first region exposed to the composition by a second area of the second region exposed to the composition.

15. A method of manufacturing an electronic device, the electronic device comprising a transistor, the transistor comprising a channel, a source and a drain spaced apart from each other and electrically connected to the channel, a gate electrode, and a gate insulating film between the gate electrode and the channel, and the method comprising: providing a barrier layer comprising a metal nitride, a metal oxynitride, or any combination thereof; providing an electrically conductive layer comprising an electrically conductive metal; and forming the gate electrode by etching a portion of the barrier layer and a portion of the electrically conductive layer by contacting the barrier layer and the electrically conductive layer with a composition according to any one of claims 1 to 9.

16. The method of claim 15, wherein the barrier layer comprises titanium nitride, titanium oxynitride, or any combination thereof, each of the titanium nitride and the titanium oxynitride optionally further comprises indium (In), aluminum (Al), lanthanum (La), scandium (Sc), gallium (Ga), silicon (Si), or any combination thereof, and the electrically conductive layer comprises tungsten (W), molybdenum (Mo), ruthenium (Ru), or any combination thereof.

17. The method of claim 15, further comprising: After the gate electrode is formed by etching a portion of the barrier layer and a portion of the conductive layer by contacting the barrier layer and the conductive layer with the composition so that an etched barrier layer and an etched conductive layer are formed, an insulating layer is provided on a surface of the etched barrier layer and a surface of the etched conductive layer.

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