Strontium compound, method for forming oxide film, method for manufacturing semiconductor device, and semiconductor device

Abstract

Disclosed are a strontium compound, a method of forming an oxide thin film, a method of manufacturing a semiconductor device, and a semiconductor device. The strontium compound is represented by Chemical Formula 1. In Chemical Formula 1, n, L1, L2, A, and m are as defined herein.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to and all benefits arising therefrom of Korean Patent Application No. 10-2024-0182020, filed on December 9, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to strontium compounds, methods for forming thin films including strontium-containing oxides, methods for manufacturing semiconductor devices including said thin films, and semiconductor devices obtained therefrom. Background Technology

[0004] Strontium, or strontium-containing oxides (e.g., strontium titanate (SrTiO3)), can be utilized, for example, in the form of nanoscale thin films, as materials in various semiconductor or microelectronic devices (e.g., high dielectric constant materials). The formation of thin films comprising strontium or strontium-containing oxides can be carried out by various methods, such as chemical vapor deposition (CVD) or atomic layer deposition (ALD). Therefore, there is interest in developing strontium-containing compounds that can be used in the preparation of thin films and the applications of such films in electronic devices. Summary of the Invention

[0005] The embodiments involve strontium-containing compounds, which can be used, for example, for thin film deposition.

[0006] The embodiments involve a strontium compound (as a precursor) for forming a strontium-containing thin film or a composition comprising said strontium compound.

[0007] The embodiments relate to a method for manufacturing strontium-containing thin films using the strontium compound.

[0008] The embodiments relate to a method of manufacturing a semiconductor device using the strontium compound.

[0009] In an embodiment, the strontium compound is represented by chemical formula 1:

[0010] Chemical Formula 1

[0011]

[0012] In chemical formula 1,

[0013] L1 is the first ligand represented by chemical formula 2.

[0014] L2 is a second ligand that is different from the first ligand.

[0015] A is a third ligand that includes oxygen or nitrogen.

[0016] n is 1 or 2, and

[0017] m can be 0, 1, 2, 3, or 4.

[0018] Chemical formula 2

[0019]

[0020] In chemical formula 2, X is nitrogen or CR, where R in CR is hydrogen or a substituted or unsubstituted C1 to C10 alkyl group.

[0021] * indicates a hydrogen or strontium (Sr) binding site (the portion bound to strontium (Sr)).

[0022] n1 is 1 or 2.

[0023] Each n² is independently 1, 2, or 3.

[0024] Each Y1 may be the same or different, and independently O or NR, wherein R in NR is hydrogen or a substituted or unsubstituted C1 to C10 alkyl group, and

[0025] R1 and R2 are each independently a substituted or unsubstituted C1 to C5 alkyl group or a Si-containing organic group.

[0026] In the implementation method, n can be 2 in chemical formula 1.

[0027] The second ligand may or may not include substituted or unsubstituted (e.g., C1-C10) alkyl groups, substituted or unsubstituted (e.g., C1-C10) alkoxy groups, substituted or unsubstituted acetylacetonate groups, substituted or unsubstituted β-diketonate moiety, substituted or unsubstituted ketoiminate moiety, substituted or unsubstituted ketostearate moiety, substituted or unsubstituted diiminate moiety, carbonyl groups, substituted or unsubstituted alkylcarbonyl groups, substituted or unsubstituted acetoxy groups, substituted or unsubstituted dialkylamido groups, or substituted or unsubstituted acetamidinate groups. The following groups are included: substituted or unsubstituted phenanthroline group, substituted or unsubstituted glyoxime group, substituted or unsubstituted carbamate group, substituted or unsubstituted cyclopentadienyl group, substituted or unsubstituted pyrrole group, substituted or unsubstituted alkoxide group, substituted or unsubstituted amidine group, substituted or unsubstituted imidazole moiety, trispyrazolyl borate moiety, or a mixture thereof.

[0028] The first ligand may be represented by chemical formula 2-1 or chemical formula 2-2:

[0029] Chemical formula 2-1

[0030]

[0031] Chemical formula 2-2

[0032]

[0033] In chemical formula 2-1 or chemical formula 2-2,

[0034] * indicates a hydrogen or strontium binding site (the portion bound to strontium).

[0035] n1 is 1 or 2.

[0036] n2 can be 1, 2, or 3 independently.

[0037] The R in CR is hydrogen or a substituted or unsubstituted C1 to C10 alkyl group.

[0038] R1 and R2 are each independently a substituted or unsubstituted C1 to C5 alkyl group, or a Si-containing organic group.

[0039] The first ligand may be represented by chemical formula 2-3 or chemical formula 2-4:

[0040] Chemical formula 2-3

[0041]

[0042] Chemical formula 2-4

[0043]

[0044] In chemical formula 2-3 or chemical formula 2-4

[0045] * indicates a hydrogen or strontium binding site (the portion bound to strontium).

[0046] n1 is 1 or 2.

[0047] n2 can be 1, 2, or 3 independently.

[0048] The Rs in CR and NR may be the same or different, and each R is independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group.

[0049] R1 and R2 are each independently a substituted or unsubstituted C1 to C5 alkyl group, or a Si-containing organic group.

[0050] The third ligand comprising oxygen or nitrogen may or may not include dialkoxyalkanes such as dimethoxyethane, tetrahydrofuran (THF), pyridine, dialkyl ethers such as diethyl ether, or combinations thereof.

[0051] The strontium compound may or may not include dimethoxyethane, THF, pyridine, diethyl ether, or combinations thereof.

[0052] The strontium compound may or may not include a third ligand containing oxygen or nitrogen.

[0053] The strontium compound can be represented by any of the following formulas.

[0054]

[0055] The strontium compound is in a liquid state at a temperature greater than or equal to about 20°C and less than or equal to about 50°C (e.g., greater than or equal to about 20°C and less than or equal to about 30°C).

[0056] The strontium compound may have a molecular weight greater than or equal to about 150 g / mol, or greater than or equal to about 300 g / mol and less than or equal to about 1,000 g / mol, or less than or equal to about 600 g / mol. For example, the strontium compound may have a molecular weight greater than or equal to about 150 g / mol and less than or equal to about 600 g / mol.

[0057] As confirmed by thermogravimetric analysis, the strontium compound can have a temperature greater than or equal to about 100°C below which the weight decreases by 10% corresponding to the total weight of the compound (i.e., T). 90% As confirmed by thermogravimetric analysis, the strontium compound may have a weight reduction of 10% corresponding to the total weight of the compound at a temperature less than or equal to about 205°C, less than or equal to about 200°C, less than or equal to about 190°C, less than or equal to about 170°C, or less than or equal to about 150°C. 90% For example, the strontium compound may have a temperature at which the weight reduction corresponds to 10% of the total weight of the compound, greater than or equal to about 100°C and less than or equal to about 170°C (i.e., T). 90% ).

[0058] As confirmed by thermogravimetric analysis, the strontium compound may have a weight reduction of 50% corresponding to the total weight of the compound at a temperature greater than or equal to about 150°C, or greater than or equal to about 180°C. 50% As confirmed by thermogravimetric analysis, the strontium compound may have a weight reduction of less than about 250°C, less than or equal to about 220°C, or less than or equal to about 200°C, corresponding to a 50% reduction in the total weight of the compound (T0). 50% For example, the strontium compound may have a temperature at which the weight decreases by 50% of the total weight of the compound, greater than or equal to about 150°C and less than or equal to about 220°C, for example, greater than or equal to about 150°C and less than or equal to about 200°C (i.e., T). 50% As confirmed by thermogravimetric analysis, the strontium compound may have a weight reduction of less than or equal to about 10% by weight, or less than or equal to about 8% by weight, based on the total weight of the compound, in a temperature range greater than or equal to about 250°C and less than or equal to about 400°C.

[0059] In one embodiment, the composition for forming a strontium-containing film includes the strontium compound. The composition may further include or may not include an organic solvent. The organic solvent may be an inert solvent that does not react with the strontium compound.

[0060] The organic solvent may include, for example, substituted or unsubstituted aliphatic hydrocarbon (e.g., alkanes, alkenes, or alkynes) solvents, substituted or unsubstituted aromatic hydrocarbon solvents, glycol dimethyl ether, polyamine solvents, or combinations thereof.

[0061] In an embodiment, the method of forming an oxide film includes performing a strontium cycle to form a strontium oxide (also referred to as a "strontium-containing oxide") or obtaining a film comprising a strontium-containing oxide.

[0062] The strontium cycle includes:

[0063] A gas, including strontium precursor gas, is supplied (e.g., by pulsed delivery) into a chamber (e.g., a process chamber) that includes a substrate.

[0064] An inert gas is supplied to the chamber to (e.g., using an inert gas) purge excess strontium precursor gas from the chamber;

[0065] The co-reactants are supplied (e.g., via pulsed delivery) to the chamber; and

[0066] Optionally, an inert gas may be supplied to the chamber to purge excess of the co-reactant from the chamber (e.g., using an inert gas).

[0067] The strontium precursor gas includes a strontium compound according to an embodiment.

[0068] The method may further include performing a first metal cycle to form a first metal oxide. The first metal cycle includes:

[0069] A gas, including a first metal precursor (gas), is supplied into the chamber;

[0070] An inert gas is supplied to the chamber to purge excess of the first metal precursor (gas) from the chamber (e.g., using an inert gas);

[0071] A first co-reactant for reacting with the first metal precursor (gas) is supplied to the chamber; and

[0072] Optionally, an inert gas is supplied to the chamber to purge excess of the first co-reactant from the chamber. The first metallic precursor may include titanium, barium, ruthenium, or a combination thereof.

[0073] The method may include multiple strontium cycles, for example, more than or equal to about 2 times (cycles) and less than or equal to about 500 times (cycles).

[0074] The method may include multiple cycles of the first metal, for example, greater than or equal to about 2 times (cycles) and less than or equal to about 500 times (cycles).

[0075] In the method, the strontium cycle and the first metal cycle can be repeated in a predetermined order or alternately.

[0076] The co-reactants may include water vapor, oxygen (oxygen gas), ozone, hydrogen peroxide, hydrogen (hydrogen gas), or combinations thereof.

[0077] The inert gas may include nitrogen, argon, helium, or a combination thereof.

[0078] In one embodiment, the method for manufacturing a semiconductor device includes:

[0079] Provides (e.g., forms) transistors integrated in or disposed on a semiconductor substrate, and

[0080] Provide (e.g., form) a capacitor electrically connected to the transistor,

[0081] Providing (e.g., forming) the transistor or providing (e.g., forming) the capacitor includes forming the oxide thin film described above.

[0082] The oxide film may include strontium oxide. The oxide film or the strontium oxide may further include a first metal. The first metal may include titanium, barium, ruthenium, or a combination thereof.

[0083] The oxide film or the strontium oxide may include strontium titanate (e.g., SrTiO3), lanthanum strontium titanate, or barium strontium titanate (e.g., Ba). x Sr 1-x TiO3, where 0 < x < 1), or combinations thereof.

[0084] The oxide thin film may include a high dielectric constant material.

[0085] The formation of the capacitor may include providing a first electrode, forming the oxide thin film, and providing a second electrode.

[0086] The formation of the transistor may include: forming a trench in a semiconductor substrate, forming the oxide thin film in the trench, and forming a gate conductor on the oxide thin film.

[0087] In an embodiment, the semiconductor device includes a semiconductor substrate, a transistor integrated in or disposed on the semiconductor substrate, and a capacitor electrically connected to the transistor, wherein at least one of the transistor or the capacitor includes a strontium-containing oxide thin film (also referred to as "thin film comprising strontium-containing oxide") formed by the methods described herein.

[0088] The strontium compounds of the embodiments can be in a liquid state at a predetermined temperature, for example, at a temperature from room temperature to about 50°C, and can exhibit relatively high vapor pressure.

[0089] In addition, when used in deposition processes (e.g., atomic layer deposition), the strontium compounds can provide process stability and can help enable the mass production of devices including strontium-containing material films with desired compositions. Attached Figure Description

[0090] The above and other advantages and features of this disclosure will become more apparent from the further detailed description of exemplary embodiments thereof with reference to the accompanying drawings, wherein:

[0091] Figure 1 This is a flowchart of a method for forming a strontium material or a strontium-containing (oxide) thin film according to an embodiment.

[0092] Figure 2 A flowchart illustrating the first metal cycle in a method for forming a strontium material or a strontium-containing (oxide) thin film according to an embodiment is shown.

[0093] Figure 3 This is a cross-sectional view of a semiconductor device according to an embodiment.

[0094] Figure 4 This is a cross-sectional view of a semiconductor device according to an embodiment. Detailed Implementation

[0095] The advantages and features of this disclosure, as well as methods for implementing it, will become apparent from the following exemplary embodiments in conjunction with the accompanying drawings. However, the invention may be embodied in many different forms, and the embodiments should not be construed as limited to those set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. The same reference numerals throughout refer to the same elements.

[0096] To clearly illustrate the contents of this disclosure, parts irrelevant to the description have been omitted, and the same reference numerals are assigned to the same or similar elements throughout the specification. In the drawings, the thickness of layers, films, panels, regions, etc., is exaggerated for clarity. Furthermore, the thickness of some layers and regions is exaggerated in the drawings for ease of description. Therefore, the embodiments described herein should not be construed as limited to the specific shapes of the regions shown herein, but rather include deviations in shape, for example, due to manufacturing processes. For example, regions illustrated or described as flat may typically have rough and / or non-linear characteristics. Furthermore, sharp corners in the illustrations may be rounded. Therefore, the regions shown in the figures are schematic in nature, and their shapes are not intended to illustrate the precise shape of the regions nor to limit the scope of the claims.

[0097] Furthermore, it will be understood that when an element, such as a layer, film, region, or substrate, is referred to as being "on" another element, it may be directly on said other element or there may be intermediate elements present. Conversely, when an element is referred to as being "directly on" another element, there are no intermediate elements present. Additionally, setting "on" a reference portion means setting it above or below the reference portion, and does not necessarily mean "above" it.

[0098] It will be understood that although the terms “first,” “second,” “third,” etc., may be used herein to describe various elements, components, regions, layers, and / or parts, these elements, components, regions, layers, and / or parts should not be limited by these terms. These terms are used only to distinguish one element, component, region, layer, or part from another. Therefore, without departing from the teachings herein, the “first element,” “component,” “region,” “layer,” or “part” discussed below may be referred to as a second element, component, region, layer, or part.

[0099] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms “a (a) (indefinite article a, an)” and “the” are intended to include the plural forms, including “at least one (a)”, unless the content clearly indicates otherwise. “At least one (a)” shall not be construed as limited to “a (a) (indefinite article a, an)”. “Or” means “and / or”.

[0100] As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items. It will be further understood that the terms “comprising” or “including” as used in this specification indicate the presence of the stated features, areas, integrals, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more additional features, areas, integrals, steps, operations, elements, components, and / or collections thereof.

[0101] In the specification, the term "in cross-section" refers to a cross-sectional view obtained by cutting the relevant portion substantially vertically (e.g., substantially vertically relative to the bottom surface) and viewing it laterally from the side.

[0102] Unless otherwise defined, all terms used herein (including technical and scientific terms) shall have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. It will be further understood that terms, such as those defined in commonly used (e.g., non-technical) dictionaries, shall be interpreted as having a meaning consistent with their meaning in the context of this disclosure and the relevant field, and shall not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0103] As used herein, unless otherwise defined, “substituted” means that at least one hydrogen atom of a compound or group is replaced by a corresponding substituent, said corresponding substituent including C1 to C30 alkyl, C2 to C30 alkenyl, C2 to C30 alkynyl, C6 to C30 aryl, C7 to C30 alkylaryl, C1 to C30 alkoxy, C1 to C30 heteroalkyl, C3 to C30 heteroaryl, C3 to C30 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C30 cycloalkynyl, C2 to C30 heterocycloalkyl, halogen (-F, -Cl, -Br, or -I), hydroxyl (-OH), nitro (-NO2), cyano (-CN), amino (-NRR', wherein R and R' are each independently hydrogen or C1 to C30 alkyl, C2 to C30 alkyl, C3 to C30 alkyl, C6 to C30 alkylaryl, C6 to C30 alkylaryl, C2 to C30 alkyl, halogen (-F, -Cl, -Br, or -I), hydroxyl (-OH), nitro (-NO2), cyano (-CN), amino (-NRR', wherein R and R' are each independently hydrogen or C1 to C30 alkyl, C2 to C30 alkyl, C3 ... C6 alkyl, azide (-N3), amidine (-C(=NH)NH2), hydrazine (-NHNH2), hydrazone (=N(NH2)), aldehyde (-C(=O)H), carbamoyl (-C(O)NH2), thiol (-SH), ester (-C(=O)OR, where R is C1 to C6 alkyl or C6 to C12 aryl), carboxyl (-COOH) or its salt (-C(=O)OM, where M is an organic or inorganic cation), sulfonic acid (-SO3H) or its salt (-SO3M, where M is an organic or inorganic cation), phosphate (-PO3H2) or its salt (-PO3MH or -PO3M2, where M is an organic or inorganic cation), or combinations thereof.

[0104] As used herein, unless otherwise defined, "hydrocarbon" or "hydrocarbon group" refers to a compound or group (e.g., alkyl, alkenyl, alkynyl, or aryl) that comprises carbon and hydrogen (e.g., composed of carbon and hydrogen). A hydrocarbon group may be a monovalent group formed by removing one or more hydrogen atoms from an alkane, alkene, alkynyl, or aromatic hydrocarbon, or a group having a valence greater than one. In a hydrocarbon or hydrocarbon group, at least one methylene group may be replaced by an oxygen moiety (-O-), a carbonyl moiety (-C(=O)-), an ester moiety (-C(=O)O-), -NH-, or a combination thereof. Unless otherwise stated to the contrary, a hydrocarbon or hydrocarbon group (alkyl, alkenyl, alkynyl, or aryl) may have 1 to 60, 2 to 32, 3 to 24, or 4 to 12 carbon atoms.

[0105] As used herein, unless otherwise defined, "alkyl" refers to a straight-chain or branched saturated monovalent hydrocarbon group (methyl, ethyl, hexyl, etc.). In embodiments, an alkyl group may have 1 to 50 carbon atoms, or 1 to 18 carbon atoms, or 1 to 12 carbon atoms.

[0106] As used herein, unless otherwise defined, "alkenyl" refers to a straight-chain or branched monovalent hydrocarbon group having a carbon-carbon double bond. In embodiments, the alkenyl group may have 2 to 50 carbon atoms, or 2 to 18 carbon atoms, or 2 to 12 carbon atoms.

[0107] As used herein, unless otherwise defined, "alkynyl" refers to a straight-chain or branched monovalent hydrocarbon group having a carbon-carbon triple bond. In embodiments, the alkynyl group may have 2 to 50 carbon atoms, or 2 to 18 carbon atoms, or 2 to 12 carbon atoms.

[0108] As used herein, unless otherwise defined, "aryl" refers to a group having a carbocyclic aromatic system. When an aryl group comprises multiple rings, the rings may be fused together. Examples include phenyl and naphthyl. In embodiments, the aryl group may have 6 to 50 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms.

[0109] As used herein, unless otherwise defined, “heterogeneous” refers to a mixture of 1 to 3 heteroatoms, such as N, O, P, Si, B, Se, Ge, Te, S, or combinations thereof.

[0110] As used herein, "heteroaryl" refers to an aromatic group having at least one N, O, P, Si, B, Se, Ge, Te, S, or a combination thereof as a cyclic atom. Examples of heteroaryls include pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, and isoquinolinyl. When a heteroaryl comprises multiple rings, the rings may be fused together. In embodiments, a heteroaryl may have 3 to 50 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms.

[0111] As used herein, unless otherwise defined, “alkoxy” refers to an alkyl group attached to an oxygen (e.g., alkyl-O-), such as methoxy, ethoxy, or sec-butoxy.

[0112] As used herein, the term "cycloalkyl" refers to a monovalent monocyclic saturated hydrocarbon group. Examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. In embodiments, the cycloalkyl group may have 3 to 50 carbon atoms, 3 to 18 carbon atoms, or 3 to 12 carbon atoms.

[0113] As used herein, the term "heterocyclic alkyl" refers to a monovalent monocyclic group that includes at least one N, O, P, Si, B, Se, Ge, Te, S, or a combination thereof as a cyclic atom in addition to the carbon atom that forms the cyclic atom. Examples include tetrahydrofuranyl and tetrahydrothiophenyl. In embodiments, the heterocyclic alkyl group may have 2 to 50 carbon atoms, 2 to 18 carbon atoms, or 2 to 12 carbon atoms.

[0114] As used herein, the term "cycloalkenyl" refers to a monovalent monocyclic hydrocarbon group having at least one carbon-carbon double bond in its ring, wherein the overall molecular structure is non-aromatic. Examples include cyclopentenyl, cyclohexenyl, and cycloheptenyl. In embodiments, the cycloalkenyl group may have 3 to 50 carbon atoms, or 3 to 18 carbon atoms, or 3 to 12 carbon atoms.

[0115] As used herein, the term "heterocyclic alkenyl" refers to a monovalent monocyclic group comprising at least one N, O, P, Si, B, Se, Ge, Te, S, or combinations thereof as cyclic atoms and at least one double bond in its ring, wherein the overall molecular structure is non-aromatic. Examples of heterocyclic alkenyl groups include 2,3-dihydrofuranyl and 2,3-dihydrothiophenylyl. In embodiments, the heterocyclic alkenyl group may have 2 to 50 carbon atoms, or 2 to 18 carbon atoms, or 2 to 12 carbon atoms.

[0116] The term "arylalkyl" refers to an alkyl group that has been substituted with an aryl group. An example of an arylalkyl group is a benzyl group (i.e., -CH2-phenyl).

[0117] The term "alkylaryl" refers to an aryl group that has been substituted with an alkyl group. An example of an alkylaryl group is tolyl.

[0118] As used herein, unless otherwise defined, “amine” is a compound represented by NR3, wherein each R is independently hydrogen, C1-C12 alkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, or C6-C18 aryl.

[0119] Unless otherwise stated, the numerical range described herein includes its endpoints. The numerical range described herein includes any real number within and including the endpoints of the stated range. In this specification, numerical endpoints, or upper or lower limits (e.g., stated as "greater than or equal to a value," "at least one value," or "less than or equal to a value," or stated as "from one value" or "to (to) a value"), may be used to form a numerical range for a given characteristic. In other words, the upper and lower endpoints of various numerical descriptions may be independently combined to provide a range.

[0120] As used herein, “about” includes the stated value and means within an acceptable range of deviations from the specific value, as determined by a person skilled in the art taking into account the measurement in question and the errors associated with the measurement of the specific quantity (i.e., limitations of the measurement system). For example, “about” may mean within one or more standard deviations relative to the stated value, or within ±10%, 5%, 3%, or 1%.

[0121] In this embodiment, a strontium precursor is provided for use in processes (e.g., chemical vapor deposition methods) for forming Sr-containing thin films (e.g., thin films comprising strontium-containing oxides). In this embodiment, the strontium precursor may be an Sr organometallic compound or an Sr coordination compound (e.g., a complex). The strontium precursor of this embodiment may exhibit improved volatility, a relatively low melting point, and / or relatively high thermal stability, and is suitable as a raw material (precursor) for thin film formation in semiconductor manufacturing processes.

[0122] In an embodiment, the strontium compound may be an organometallic complex comprising an organic group (e.g., a ligand) and strontium.

[0123] The strontium compound can be represented by chemical formula 1:

[0124] Chemical Formula 1

[0125]

[0126] In chemical formula 1,

[0127] L1 is the first ligand represented by chemical formula 2.

[0128] L2 is a second ligand that is different from the first ligand (e.g., a monoanion ligand).

[0129] A is a third ligand that includes oxygen or nitrogen.

[0130] n is 1 or 2, and

[0131] m ranges from 0 to 4.

[0132] Chemical formula 2

[0133]

[0134] In chemical formula 2, X is nitrogen or CR (where R in CR is hydrogen or a substituted or unsubstituted C1 to C10 alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, etc.).

[0135] * indicates a hydrogen or strontium (Sr) binding site.

[0136] n1 is 1 or 2.

[0137] Each n² is an independent integer from 1 to 3 (e.g., 1, 2, or 3).

[0138] Each Y1 in NR may be the same or different and is independently oxygen or NR (where R is hydrogen or a substituted or unsubstituted C1 to C10 alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, or pentyl).

[0139] R1 is a substituted or unsubstituted C1 to C5 alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, or isopentyl) or a Si-containing organic group (e.g., trialkylsilyl such as Si(CH3)3), and

[0140] R2 is a substituted or unsubstituted C1 to C5 alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, or isopentyl) or a Si-containing organic group (e.g., a trialkylsilyl group such as Si(CH3)3). R1 ​​and R2 may be the same or different.

[0141] Strontium oxide films can have a perovskite structure exhibiting paraelectric properties. In embodiments, strontium oxide (e.g., SrTiO3) films deposited by atomic layer deposition (ALD) can achieve a dielectric constant of about 150 or greater and can exhibit step (staircase) coverage within the pattern with a desired degree of thickness and composition. Therefore, various Sr-containing films (e.g., SrTiO3-containing films) can be used as materials with high dielectric constants, for example, in next-generation DRAM capacitors.

[0142] Thin films can be formed using various methods such as sputtering, ion plating, thermal decomposition, sol-gel, metal-organic deposition (MOD), or chemical vapor deposition (CVD). ALD (atomic layer deposition) or CVD processes are suitable for semiconductor device fabrication in terms of compositional controllability, step coverage, large-scale production rates, and hybrid integration capabilities. Few precursor materials for Sr atomic sources used in CVD have been reported; however, these compounds suffer from the problem of unstable deposition processes due to the low volatility, high melting point, and low thermal stability of strontium compounds, which belong to the alkaline earth metal group.

[0143] For example, Sr(iPr3Cp)2 (bis(1,2,4-tris-isopropylcyclopentadienyl)strontium) has been used relatively widely as a strontium precursor. While the vapor pressure for deposition can be achieved by heating the canister to approximately 100°C, Sr(iPr3Cp)2 exhibits high reactivity, which can raise concerns about excessive initial growth. Furthermore, Sr(iPr3Cp)2 is a solid phase over a temperature range from room temperature to approximately 50°C, which can make it difficult to provide the desired level of conformality within high aspect ratio DRAM capacitor structures.

[0144] In related technologies (prior art), the types of strontium-containing feedstocks or precursors available for deposition processes are limited, and there are some difficulties in using such materials in deposition processes. Most strontium precursors available in related technologies are solid-phase materials with very low vapor pressures. In order to provide the desired level of vapor pressure in the process with such strontium precursors, it may be necessary to heat the tanks and pipelines to relatively high temperatures, which may require the use of high-temperature tanks and high-temperature valves, or alternatively, a liquid delivery system (LDS) method involving solvent dissolution may be required. The inventors have found that strontium precursors in related technologies can have the following problems: contamination caused by condensation of the precursor at cold points or within valves makes process or equipment maintenance difficult.

[0145] For example, Sr(iPr3Cp)2 can be heated to approximately 100°C to obtain a vapor pressure suitable for deposition; however, its high reactivity raises concerns about excessive initial growth. The inventors have also found that Sr(iPr3Cp)2 can be a solid phase under desired deposition conditions, and can present difficulties in providing the desired level of conformity within high aspect ratio DRAM capacitor structures. Furthermore, moderate reactivity of the strontium precursor is desirable in terms of suppressing excessive initial growth and achieving low impurity content.

[0146] The molecular size of strontium precursors needs to be controlled for step coverage and suitability for large-scale production. Therefore, ALD processes using strontium precursors are currently highly challenging. Furthermore, from a large-scale production perspective, the development of strontium precursors in the liquid phase or with sufficient vapor pressure, and the development of ALD processes using such precursors, is desirable.

[0147] The strontium compounds according to the embodiments can solve one or more of the aforementioned process technology problems. The strontium compounds of the embodiments can exhibit a liquid phase at temperatures of about 20°C to about 50°C or about 25°C to about 35°C (e.g., at room temperature). Furthermore, as confirmed by thermogravimetric analysis results, they are expected to provide desired levels of vapor pressure in semiconductor device manufacturing processes (e.g., thin film deposition processes or ALD processes).

[0148] In embodiments, the first ligand may have two or more oxygen atoms, together with the oxygen atom directly bonded (binded) to strontium. In addition to direct bonding to strontium (see O marked with *) (e.g., via covalent bonding), the oxygen atoms (corresponding to O in Y1) may also have additional interactions with strontium (e.g., interacting with strontium via lone pair electrons to form coordinate bonds), contributing to increased metal coverage through the ligand. In embodiments, the first ligand may be represented by chemical formula 2-1 or chemical formula 2-2:

[0149] Chemical formula 2-1

[0150]

[0151] Chemical formula 2-2

[0152]

[0153] In chemical formula 2-1 or chemical formula 2-2,

[0154] * indicates a hydrogen or strontium binding site.

[0155] n1 is 1 or 2.

[0156] The R in CR is hydrogen or a substituted or unsubstituted C1 to C10 alkyl group.

[0157] Each n² is an independent integer from 1 to 3 (e.g., 1, 2, or 3).

[0158] R1 can be a substituted or unsubstituted C1 to C5 alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, or isopentyl) or a Si-containing organic group, and

[0159] R2 can be a substituted or unsubstituted C1 to C5 alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, or isopentyl) or a Si-containing organic group. R1 and R2 can be the same or different. It will be understood that when propyl and isopropyl are mentioned together, "propyl" can mean n-propyl; when butyl and isobutyl are mentioned together, "butyl" can mean n-butyl; and when pentyl and isopentyl are mentioned together, "pentyl" can mean n-pentyl.

[0160] In the first ligand with such a structure, the oxygen atom can be covalently bonded to the strontium atom, or can interact with the strontium atom through lone pair electrons (e.g., forming a coordinate bond).

[0161] In embodiments, the first ligand may comprise two, three, or more nitrogen atoms, and the nitrogen atoms (N in Y1) may have additional interactions with strontium (e.g., interacting with strontium atoms via lone pair electrons to form coordinate bonds), contributing to increased metal coverage through the ligand. In embodiments, the first ligand may be represented by chemical formula 2-3 or chemical formula 2-4:

[0162] Chemical formula 2-3

[0163]

[0164] Chemical formula 2-4

[0165]

[0166] In chemical formula 2-3 or chemical formula 2-4

[0167] * indicates a hydrogen or strontium binding site.

[0168] n1 is 1 or 2.

[0169] Each n2 is an independent integer from 1 to 3 (e.g., 1, 2, or 3).

[0170] The R in CR and NR is independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group.

[0171] R1 can be a substituted or unsubstituted C1 to C5 alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, or isopentyl) or a Si-containing organic group, and

[0172] R2 can be a substituted or unsubstituted C1 to C5 alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, or isopentyl) or a Si-containing organic group. R1 and R2 can be the same or different.

[0173] In the first ligand with such a structure, the nitrogen atom can interact with the strontium atom via lone pair electrons (e.g., forming a coordinate bond).

[0174] In embodiments, in the strontium compounds described herein, the Si-containing organic group may be, for example, an alkylsilyl group having one or more, two or more, or three or more substituted or unsubstituted C1 to C10 or C2 to C3 alkyl groups, such as methyl, ethyl, or propyl. Examples include, but are not limited to, substituted or unsubstituted trimethylsilyl, substituted or unsubstituted triethylsilyl, and substituted or unsubstituted diethylmethylsilyl.

[0175] As mentioned above, in the above chemical formulas, R1 may be the same as or different from R2. In R1 and R2, C1 to C5 alkyl groups may be substituted with halogen groups, amino groups, hydroxyl groups, alkoxy groups, etc., but are not limited to these.

[0176] Strontium compounds according to embodiments may include a first ligand having the structure described herein as a ligand in a manner described herein. For example, in the first ligand of formula 2, n1 within a defined range ensures an appropriate distance between the strontium and the first ligand, thereby providing increased shielding or metal coverage for the strontium and reducing interactions between the final precursor molecules.

[0177] Furthermore, in the first ligand of Formula 2, the introduction of a flexible alkyl group increases entropy, and the non-conjugated structure minimizes intermolecular interactions. The first ligand of Formula 2 includes lone pairs of electrons, which can increase the metal coverage through the ligand and contribute to the stabilization of the strontium atom.

[0178] In the case of strontium precursors in related technologies, due to the large size of strontium atoms, interactions between precursor molecules can easily occur, causing the molecules to exist as dimers or oligomers. This can lead to an increase in the melting point and viscosity of the precursor compound, as well as a decrease in vapor pressure.

[0179] In the strontium precursor according to embodiments, including a first ligand in a manner described herein may contribute to improved ligand metal coverage, enhanced precursor stability, and reduced interactions between strontium precursors.

[0180] Therefore, strontium compounds of embodiments having such a structure can exist in a liquid state at a predetermined temperature (e.g., from room temperature to about 50°C) without any special treatment. Furthermore, for example, as confirmed by thermogravimetric analysis or other suitable analytical methods, the strontium compounds of the embodiments are expected to provide a higher vapor pressure than strontium precursors of related technologies under thin-film deposition process conditions.

[0181] Strontium has a relatively large atomic size. Without being bound by any theory, it is considered that this large size, as an alkaline earth metal, can lead to significant intermolecular interactions between precursor molecules, even in the presence of ligand coordination. This can result in increased melting point, increased viscosity, and decreased vapor pressure. Therefore, ligands according to related technologies can present difficulties in adequately coordinating with such strontium atoms to provide the desired properties.

[0182] Conversely, in the case of the strontium compound in the embodiments, the introduction of the first ligand can reduce the intermolecular interactions between strontium precursors to a desired level by sufficiently shielding the central strontium atom, thereby enabling an increase in the vapor pressure and liquefaction of the precursors. The introduction of the first ligand can lead to an increase in the metal (Sr) coverage of the central metal (i.e., strontium) in the precursors.

[0183] In an embodiment, n in Formula 1 may be 2, and in this case, the strontium compound may include a first ligand but no second ligand.

[0184] The strontium compound of the embodiments may have one or more, for example, two first ligands. In embodiments, the strontium compound may further include a second ligand different from the first ligand. The second ligand may be a monoanionic ligand having a chemical structure different from that of the first ligand. The strontium precursor of the embodiments may or may not include the second ligand (n is 2).

[0185] The second ligand may include substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted acetylacetone groups, substituted or unsubstituted β-diketone moieties (e.g., substituted or unsubstituted heptanedione moieties, substituted or unsubstituted acetylacetone moieties, or substituted or unsubstituted octanedione moieties), substituted or unsubstituted β-ketoimine moieties (e.g., aminopentenoate moieties), substituted or unsubstituted β-ketostearate moieties, substituted or unsubstituted β-diimine moieties, carbonyl groups, etc. Substituted or unsubstituted alkyl carbonyl group, substituted or unsubstituted acetoxy group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted acetamidine group, substituted or unsubstituted phenanthroline group, substituted or unsubstituted dioxime group, substituted or unsubstituted carbamate group, substituted or unsubstituted cyclopentadienyl group, substituted or unsubstituted pyrrole group, substituted or unsubstituted alcohol group, substituted or unsubstituted amidine group, substituted or unsubstituted imidazole moiety, tripyrazolylborate moiety, or combinations thereof.

[0186] The second ligand can be represented by the following formula, but is not limited to the following formula:

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193] In the above formula, * represents the binding site with strontium.

[0194] In Formula 1, A is a third ligand comprising oxygen or nitrogen. The third ligand having oxygen or nitrogen can be introduced from a solvent or the like used in the synthesis of the precursor (e.g., a solvate portion). Such a third ligand can be removed by a post-synthetic removal process.

[0195] In embodiments, the third ligand may include, but is not limited to, dialkoxyalkanes such as dimethoxyethane, tetrahydrofuran, pyridine, dialkyl ethers such as diethyl ether, or combinations thereof. The strontium compounds of the embodiments may further include or may not include the third ligand. The strontium compounds of the embodiments may include or may not include dimethoxyethane (glycol dimethyl ether), THF, pyridine, diethyl ether, or combinations thereof.

[0196] In an embodiment, the strontium compound may be represented by one of the following formulas:

[0197]

[0198] The strontium compounds of the embodiments exhibit reduced intermolecular interactions and are liquid at room temperature, and therefore can be used as strontium precursors in various deposition processes, for example, supplied with or without a carrier gas. The strontium compounds are liquid at temperatures greater than or equal to about 20°C and less than or equal to about 50°C.

[0199] The strontium compounds of the embodiments, as confirmed by thermogravimetric analysis, may have a temperature greater than or equal to about 100°C below which a 10% weight loss occurs (i.e., below which the residual weight is 90%). 90% .

[0200] The strontium compound may have a molecular weight greater than or equal to about 150 g / mol, greater than or equal to about 180 g / mol, greater than or equal to about 190 g / mol, greater than or equal to about 200 g / mol, greater than or equal to about 250 g / mol, greater than or equal to about 280 g / mol, greater than or equal to about 300 g / mol, greater than or equal to about 350 g / mol, greater than or equal to about 400 g / mol, greater than or equal to about 410 g / mol, greater than or equal to about 440 g / mol, or greater than or equal to about 450 g / mol. The strontium compound may have a molecular weight less than or equal to about 1,000 g / mol, less than or equal to about 800 g / mol, less than or equal to about 600 g / mol, less than or equal to about 550 g / mol, or less than or equal to about 500 g / mol.

[0201] As confirmed by thermogravimetric analysis, the strontium compound may have a temperature (T0) greater than or equal to about 100°C, greater than or equal to about 120°C, greater than or equal to about 130°C, greater than or equal to about 140°C, or greater than or equal to about 150°C, below which the weight (mass) loss is 10% of the total weight of the compound. 90% The strontium compound may have a temperature (T0) less than or equal to about 205°C, less than or equal to about 200°C, less than or equal to about 190°C, less than or equal to about 180°C, less than or equal to about 170°C, less than or equal to about 160°C, or less than or equal to about 150°C, below which the weight (mass) loss is 10% of the total weight of the compound. 90% ).

[0202] As confirmed by thermogravimetric analysis, the strontium compound may have a temperature (T0) greater than or equal to about 150°C, greater than or equal to about 160°C, greater than or equal to about 170°C, greater than or equal to about 180°C, greater than or equal to about 185°C, or greater than or equal to about 190°C, below which the weight (mass) loss is 50% of the total weight of the compound. 50% The strontium compound may have a temperature (T0) below which the weight (mass) loss is 50% of the total weight of the compound, below about 250°C, less than or equal to about 240°C, less than or equal to about 230°C, less than or equal to about 220°C, less than or equal to about 215°C, less than or equal to about 210°C, less than or equal to about 205°C, or less than or equal to about 200°C. 50% ).

[0203] As confirmed by thermogravimetric analysis, the strontium compound may have a slope greater than or equal to about -2, greater than or equal to about -1.7, greater than or equal to about -1.5, greater than or equal to about -1.4, greater than or equal to about -1.3, greater than or equal to about -1.2, greater than or equal to about -1.1 and less than about 0, or less than or equal to about -0.5, as defined by the following equation:

[0204] Slope = dW / dT

[0205] Where dW represents the change in weight and dT represents the change in temperature.

[0206] The slope can be the weight change according to temperature, and a larger absolute value of the slope may indicate that the corresponding strontium compound is more volatile.

[0207] As confirmed by thermogravimetric analysis, the strontium compound exhibits the following weight loss at temperatures between about 250°C and about 400°C: less than or equal to about 10% by weight, less than or equal to about 9% by weight, less than or equal to about 8% by weight, less than or equal to about 7% by weight, less than or equal to about 6% by weight, less than or equal to about 5% by weight, less than or equal to about 4% by weight, less than or equal to about 3% by weight, less than or equal to about 2% by weight, less than or equal to about 1% by weight, or less than or equal to about 0.5% by weight.

[0208] Unbound by any theoretical constraints, the strontium compounds of the embodiments may exhibit, for example, thermal behaviors different from those of strontium precursors according to related technologies, as confirmed by thermogravimetric analysis. This may indicate that the strontium compounds of the embodiments exhibit relatively lower vaporization temperatures (evaporation temperatures), improved vapor pressure characteristics, and enhanced process stability. In the embodiments, the relatively low TV observed in thermogravimetric analysis... 50% and T 90% The value indicates that the strontium compound of the embodiment exhibits higher volatility and therefore increased vapor pressure.

[0209] The strontium compounds of the embodiments can be suitably synthesized using known chemical reactions involving commercially available reagents. For example, the strontium compounds of the embodiments can be prepared by reacting a first reagent comprising a first ligand moiety and a reactive group, a second reagent comprising a second ligand moiety and a reactive group, and a strontium-containing reagent in a suitable solvent. The method for synthesizing the first reagent can be recognized by those skilled in the art by referring to the method provided in the preparation examples, and the second reagent can be commercially available or readily obtained by known methods.

[0210] Examples of strontium-containing reagents may include, but are not limited to, Sr(HMDS)2 (bis[bis(trimethylsilyl)amide]strontium). Strontium-containing reagents may also be commercially available or readily synthesized by known methods.

[0211] Organic solvents may include, for example, substituted or unsubstituted aliphatic hydrocarbon solvents (e.g., alkanes such as hexane, octane, or heptane; alkenes; or alkynes), substituted or unsubstituted aromatic hydrocarbon solvents such as toluene, ether solvents such as glycol dimethyl ether, THF, or diethyl ether, pyridine, polyamine solvents, or combinations thereof.

[0212] The strontium compounds of the embodiments can be in a liquid state at a predetermined temperature (e.g., at a temperature of about 20°C to about 50°C) and can exhibit an increased vapor pressure level. Therefore, the strontium compounds of the embodiments can be used in the formation of thin films by vapor deposition processes (e.g., in the formation of oxide or high dielectric constant material thin films during semiconductor device manufacturing).

[0213] Therefore, the embodiments relate to a method of manufacturing a thin film using the strontium compound.

[0214] In embodiments, thin film formation using the strontium compound may include chemical vapor deposition (CVD) or atomic layer deposition (ALD) processes. CVD processes utilize volatile compounds that can be evaporated and continuously introduced into the deposition chamber. Precursor compounds may chemically react in the gas phase or directly on a heated substrate to form a film of the desired material, while undesirable volatile components may be removed by vacuum pumping or inert gas purging. In the case of CVD, single-source precursors (SSPs) or multi-source precursors may be used to fabricate the desired material film. The strontium compound of the embodiments can be used in CVD processes to form a material thin film having a desired composition.

[0215] In embodiments, the formation of thin films using the strontium compound may involve atomic layer deposition (ALD). In the methods of embodiments, the atomic layer deposition technique may involve two alternating surface reactions for thin film formation.

[0216] In the ALD implementation, the surface of the substrate can be sequentially exposed to the precursor and co-reactant (reactant), and if desired, an inert gas such as argon (Ar) or nitrogen (N2) can be used to separate the two surface reactions. Once the surface of the substrate becomes saturated by exposure to the precursor (or co-reactant) in each step, no further reaction occurs.

[0217] Through this self-limiting thin film growth mechanism, the method involving ALD can achieve excellent conformability, uniform coverage, and precise thickness control. In the method of this embodiment, ALD can be performed in a cyclic manner.

[0218] In an embodiment, the growth cycle (i.e., each growth cycle) may include: implanting a precursor; exposing the substrate to the precursor; purging and exhausting to remove excess precursor and byproducts; implanting and exposing the co-reactant; and purging and exhausting to remove excess co-reactant and byproducts. In the method of this embodiment, the ALD or growth cycle may be repeated a predetermined number of cycles to deposit a desired film thickness. Therefore, in ALD technology, precise control of the film thickness can be achieved depending on the number of cycles.

[0219] The time required for one cycle can range from a few seconds to several minutes, depending on (1) the purpose of the process, (2) the chemical properties of the precursors used, (3) the substrate structure and deposition temperature, and (4) the reactivity between the substrate and the precursors, and there are no particular limitations. Each cycle can be designed taking into account the interaction between the precursors and co-reactants, as well as the geometry of the substrate to be used. In embodiments, the terms "excess precursor" and "excess co-reactant" can refer to a portion of the corresponding species remaining in the reaction space after the completion of the self-confined surface reaction, and may include unreacted gaseous species, weakly physically adsorbed species, and / or volatile byproducts.

[0220] Therefore, in this embodiment, the method for forming an oxide thin film includes performing a strontium cycle to form a strontium oxide. The strontium cycle includes:

[0221] A gas containing a strontium precursor (hereinafter referred to as "strontium precursor gas") is supplied (e.g., by pulse delivery) into a chamber (e.g., a process chamber) containing a substrate (S101);

[0222] An inert gas is supplied to the chamber to purge excess strontium precursor gas (S102), for example, using an inert gas; and

[0223] The co-reactant is supplied (e.g., by pulse delivery) into the chamber (S103).

[0224] The strontium precursor gas or the strontium precursor comprises a strontium compound according to an embodiment. An inert gas may or may not be used as a carrier gas in the supply of the strontium precursor. The strontium precursor gas may be a vaporized strontium compound according to an embodiment. In an embodiment, the strontium precursor gas may not include an inert gas. The method may further include supplying an inert gas into a chamber to purge excess co-reactant (S104) (e.g., using an inert gas) (see...). Figure 1 ).

[0225] The supply of the strontium precursor gas can be carried out by suitable methods known to those skilled in the art of deposition, and is not particularly limited thereto. The supply of the strontium precursor gas may include the use of a composition for thin film formation. In embodiments, the composition for thin film formation includes the strontium compound. The composition may further include or may not include an organic solvent. The organic solvent may be an inert solvent that does not react with the strontium compound. There are no particular limitations on the organic solvent, and any solvent listed above as a reaction solvent may be used. In embodiments, the organic solvent may include, but is not limited to, toluene, hexane, octane, etc.

[0226] The supply of strontium precursor gas may include evaporating a composition for thin film formation stored in a container to form vapor by heating or by depressurization, and supplying the vapor to a chamber in which a substrate is placed. In one embodiment, the composition for forming the thin film may be supplied in a liquid state to a vaporization chamber, and in the vaporization chamber, the composition may be vaporized by heating or depressurization to form vapor, which is then supplied to a chamber in which the substrate is placed.

[0227] The strontium precursor gas can be supplied using a carrier gas. In an embodiment, the liquid precursor can be evaporated by optionally bubbling the carrier gas through it under heating. Since the strontium compound (i.e., the precursor) of the embodiment is in a liquid state under the conditions of the method of the embodiment, it is advantageous for evaporation. The carrier gas can be suitably selected and may include an inert gas, such as nitrogen, argon, or helium.

[0228] The strontium precursor supplied to the chamber can react with the substrate and adsorb onto the substrate. When all reactive sites on the substrate are saturated with the strontium precursor, the remaining excess strontium precursor and byproducts can be removed in a subsequent purging step (S102).

[0229] The co-reactant can then be supplied (e.g., pulsed delivery) into the process chamber. The co-reactant reacts with a strontium precursor adsorbed on the substrate to form a thin film of a strontium-containing material (e.g., strontium oxide). In some embodiments, including plasma enhancement, the co-reactant can be ignited by plasma.

[0230] Through the reaction with the co-reactant, all reactive sites on the substrate surface can be consumed, and at this point, the chamber can be purged again using an inert carrier gas (S104). Subsequently, it can be determined whether the film formed on the substrate has reached the desired thickness or composition, and if the desired thickness or composition has not been achieved, the strontium cycle can be repeated until the film formed on the substrate reaches the desired thickness.

[0231] The method may further include a first metal cycle for forming a first metal oxide. The first metal cycle includes:

[0232] A gas comprising a first metal precursor (hereinafter referred to as the first metal precursor gas) is supplied into a chamber (e.g., a process chamber) (S201);

[0233] An inert gas is supplied into the chamber to purge excess first metal precursor (gas) (S202); and

[0234] The first co-reactant is supplied into the chamber to react with the first metal precursor (gas) (S203).

[0235] The first metal cycle may further include supplying an inert gas into the chamber to purge excess first co-reactant (S204). The first metal precursor may include titanium, barium, ruthenium, or combinations thereof.

[0236] The type of the first metal precursor is not particularly limited and can be appropriately selected. The first metal precursor may include, but is not limited to, metal alkoxides or organometallic ammonium salts. When the first metal precursor includes titanium, it may include titanium compounds such as Ti(OiPr)4, Ti(OtBu)4, Ti(NMe2)4, Ti(NEtMe)4, or Ti(NEt2)4, but is not limited to these. Here, iPr means isopropyl, tBu means tert-butyl, Me means methyl, and Et means ethyl.

[0237] The preparation and supply of the gas for the first metal precursor can be carried out with reference to the description provided above for the strontium precursor.

[0238] The method may include multiple strontium cycles. The method may also include multiple first metal cycles. In the method, taking into account the composition of the film to be formed, the strontium cycles and the first metal cycles may be repeated alternately or sequentially in a predetermined order, but the order is not particularly limited.

[0239] The strontium compounds of the embodiments and the thin film formation methods using them can be used in the manufacture of semiconductor devices (e.g., capacitors or transistors), for example, to form dielectric layers (dielectric layers) or insulating layers.

[0240] Therefore, in the embodiments, the method for manufacturing a semiconductor device includes:

[0241] Provide or form transistors integrated into or disposed on a semiconductor substrate; and

[0242] Provide or form a capacitor that is electrically connected to the transistor.

[0243] At least one of providing (or forming) a transistor or providing (or forming) a capacitor includes forming the thin film described above (e.g., a thin film containing strontium material or a thin film containing strontium oxide) according to the deposition method described herein.

[0244] The oxide film may include strontium oxide. The oxide film or strontium oxide may further include a first metal. The first metal may include titanium, barium, ruthenium, or a combination thereof.

[0245] Oxide films or strontium oxides may include strontium titanate (SrTiO3), lanthanum strontium titanate, and barium strontium titanate [Ba x Sr 1-x TiO3 (where 0 < x < 1) or combinations thereof.

[0246] Oxide films may include materials with high dielectric constants.

[0247] In a method for manufacturing a semiconductor device according to an embodiment, the formation of a capacitor may include forming or providing a first electrode, forming an oxide thin film, and forming or providing a second electrode. The formation of the oxide thin film (or dielectric film) may be performed according to the thin film formation method described herein. The capacitor may be formed along the contour of the first electrode. The formation of the capacitor dielectric layer can be referred to... Figure 1 and Figure 2 The flowchart illustrates this. A second electrode may be formed or provided on the dielectric layer of the formed capacitor. There are no particular limitations on the methods for forming the first and second electrodes, and they may be appropriately selected.

[0248] In an embodiment, forming a transistor may include forming a trench in a semiconductor substrate, forming an oxide thin film within the trench, and forming or providing a gate conductor on the oxide thin film. The formation of the oxide thin film (or gate insulating film) may be performed according to the thin film formation methods described herein, for example, referring to… Figure 1 and Figure 2 .

[0249] In an embodiment, the semiconductor device includes a semiconductor substrate, a transistor integrated into or disposed on the semiconductor substrate, and a capacitor electrically connected to the transistor. At least one of the transistor or capacitor includes a strontium-containing oxide film (e.g., formed by the methods described herein). The oxide film can be used as a dielectric layer, insulating layer, passivation layer, and / or protective layer in various devices. The device can be, for example, a semiconductor device or a display device.

[0250] In the following description, examples of semiconductor devices according to embodiments will be described with reference to the accompanying drawings.

[0251] Figure 3 This is a cross-sectional view showing an example of a semiconductor device according to an embodiment.

[0252] Reference Figure 3The semiconductor device 500 according to the embodiment includes a semiconductor substrate 110, a transistor 200, and a capacitor 100. At least one of the transistor 200 or the capacitor 100 may include an oxide film, and the oxide film may be formed by the methods described above. The oxide film may be a strontium oxide film.

[0253] The semiconductor substrate 110 may include silicon; germanium; silicon-germanium; III-V compounds such as GaP, GaAs, or GaSb; or combinations thereof. In embodiments, the semiconductor substrate 110 may be a silicon-on-insulator (SOI) substrate or a germanium-on-insulator (GOI) substrate.

[0254] Transistor 200 may be located in an active region defined by shallow trench isolation (STI) 130 in semiconductor substrate 110 and may be electrically connected to bit line 120 and capacitor 100 to serve as a switching element. Transistor 200 may be a field-effect transistor (FET), which includes a source region 173, a drain region 175, a gate electrode 124, and a gate insulating film 140. Field-effect transistors (FETs) may have various structures and may be, for example, FinFET, GAAFET, MBCFET, CFET, or VFET, but are not limited thereto.

[0255] In this embodiment, source region 173 and drain region 175 are provided in semiconductor substrate 110 and are spaced apart from each other along the in-plane direction of semiconductor substrate 110. Source region 173 and drain region 175 may be conductive regions in semiconductor substrate 110 highly doped with p-type or n-type impurities. In the case of an n-type transistor, source region 173 and drain region 175 may be highly doped with n-type impurities, and in the case of a p-type transistor, source region 173 and drain region 175 may be highly doped with p-type impurities. Source region 173 may be electrically connected to capacitor 100, and drain region 175 may be electrically connected to bit line 120.

[0256] The gate electrode 124 may be formed on the semiconductor substrate 110 and may be located between the source region 173 and the drain region 175. The gate electrode 124 may comprise a low-resistance conductive material, and may comprise, for example, Ti, TiN, TiON, or combinations thereof, but is not limited thereto. The gate electrode 124 may be formed as a single layer or as two or more layers.

[0257] The gate insulating film 140 may be located between the gate electrode 124 and the semiconductor substrate 110, and may include an oxide film according to embodiments described herein. The gate insulating film 140 may include an oxide film formed by methods involving atomic layer deposition, and may be, for example, a strontium oxide film. A detailed description of strontium oxide films is provided herein.

[0258] Interlayer insulating films 160 and 180 may be formed above the transistor. Interlayer insulating films 160 and 180 may include, but are not limited to, oxides, nitrides, oxynitrides, or combinations thereof comprising, for example, silicon, aluminum, hafnium, lanthanum, zirconium, tantalum, yttrium, titanium, barium, strontium, or alloys thereof. Interlayer insulating films 160 and 180 have a plurality of contact holes, and the contact holes are filled with a conductive material to form a plurality of contacts 161, 162, and 150.

[0259] Bit line 120 may be formed between interlayer insulating films 160 and 180. Bit line 120 may be electrically connected to drain region 175 of transistor 200 via contact 162. Bit line 120 may be configured to intersect word line (not shown), and multiple arrays may be formed by bit line 120 and word line. Word line may be electrically connected to gate electrode 124.

[0260] Capacitor 100 may be embedded in (buried in) interlayer insulating film 180, and more particularly, may be formed in trench 181 provided in interlayer insulating film 180. The shape of trench 181 is not particularly limited, and for example, the connection portion between the bottom surface and side surface of trench 181 may have a circular shape, or the side surface of trench 181 may be inclined at a predetermined angle. Trench 181 may have a high aspect ratio, and the higher the aspect ratio, the greater the capacitance of capacitor 100. Capacitor 100 may be electrically connected to the source region 173 of transistor 200 via contact 161.

[0261] The capacitor 100 includes a first electrode 10, a dielectric film 30, and a second electrode 20.

[0262] The first electrode 10 may be disposed within the trench 181 along the inner wall of the interlayer insulating film 180. The first electrode 10 may be a thin film, and for example, may be a continuous thin film formed with substantially uniform thickness within the trench 181 along the inner wall of the interlayer insulating film 180. For example, the first electrode 10 may be formed by atomic layer deposition (ALD).

[0263] The dielectric film 30 may comprise a thin film (e.g., an oxide film or a strontium oxide film) formed by the thin film formation methods described herein (e.g., involving atomic layer deposition). The oxide film or strontium oxide film may comprise strontium titanate (SrTiO3), lanthanum strontium titanate, barium strontium titanate [Ba...] x Sr 1-x TiO3 (where 0 < x < 1) or combinations thereof.

[0264] The dielectric film 30 may be disposed above the first electrode 10 within the trench 181 along the inner wall of the interlayer insulating film 180, and may be a continuous thin film formed, for example, within the trench 181 along the inner wall of the interlayer insulating film 180 with a substantially uniform thickness. The thickness of the dielectric film 30 may be from about 1 nm to 100 nm, and within this range, it may be from about 2 nm to 80 nm, from about 2 nm to 50 nm, or from about 2 nm to 30 nm.

[0265] The second electrode 20 may fill the interior of the trench 181. However, it is not limited thereto, and the second electrode 20 may fill a portion of the trench 181 and be filled thereon with a filler material. The second electrode 20 may include, for example, a metal, a metal nitride, a metal oxynitride, or a combination thereof, and may include, for example, Ti, TiN, TiON, TaN, MoN, CoN, TiAlN, TaAlN, W, Ru, Ir, IrO2, Pt, or a combination thereof, but is not limited thereto.

[0266] Contact 150 may be located within interlayer insulating film 180, and through contact 150, bit line 120 and upper wiring layer may be electrically connected. Barrier layer 170 may be formed around contact 150.

[0267] One or more interlayer insulating films 190 and 195 may be located above capacitor 100, and capacitor 100 may be electrically connected to wiring (not shown) embedded in interlayer insulating films 190 and 195.

[0268] Figure 4 This is a cross-sectional view showing another example of a semiconductor device according to an embodiment.

[0269] Reference Figure 4 As in the examples described above, the semiconductor device 500 according to the embodiments includes a semiconductor substrate 110, a transistor 200, and a capacitor 100. At least one of the transistor 200 and the capacitor 100 may comprise a thin film (e.g., an oxide film or a strontium oxide film) formed by the thin film formation method described herein (e.g., atomic layer deposition). The oxide film or strontium oxide film may include strontium titanate (SrTiO3), lanthanum strontium titanate, barium strontium titanate [Ba... x Sr 1-x TiO3 (where 0 < x < 1) or combinations thereof.

[0270] In one embodiment, the semiconductor device 500 according to the embodiment may include a transistor 200 having a BCAT (buried cell array transistor) structure, wherein the gate electrode 124 and the gate insulating film 140 are embedded in the semiconductor substrate 110, but is not limited thereto.

[0271] The transistor 200 has a plurality of trenches 111. The trenches 111 are formed at a predetermined depth from the surface of the semiconductor substrate 110 and expose the inner wall of the semiconductor substrate 110. The shape of the trenches 111 is not particularly limited, and for example, the connection between the bottom surface and the side surface of the trench 111 may have a circular shape, or the side surface of the trench 111 may be inclined at a predetermined angle.

[0272] A gate insulating film 140 is disposed within the trench 111 along the inner wall of the semiconductor substrate 110. The gate insulating film 140 may comprise the thin film described above, and may be, for example, a strontium-containing oxide thin film as described herein. The oxide thin film or the strontium oxide thin film may include strontium titanate (SrTiO3), lanthanum strontium titanate, barium strontium titanate [Ba...]. x Sr 1-x TiO3 (where 0 < x < 1) or combinations thereof, as described herein. The gate insulating film 140 may be a continuous thin film of substantially uniform thickness formed, for example, within the trench 111 along the inner wall of the semiconductor substrate 110 by the atomic layer deposition method described above. The thickness of the gate insulating film 140 may be from about 1 nm to 30 nm, and within this range, it may be from about 3 nm to 20 nm or from about 5 nm to 10 nm.

[0273] The gate electrode 124 may fill a portion of the trench 111. However, the gate electrode 124 is not limited to this and may also be a continuous thin film disposed above the gate insulating film 140 within the trench 111 along the inner wall of the semiconductor substrate 110. The gate electrode 124 may comprise a low-resistance conductive material and may comprise, for example, Ti, TiN, TiON, or combinations thereof. The thickness of the gate electrode 124 may be from about 1 nm to 30 nm, and within this range, it may be from about 3 nm to 20 nm or from about 5 nm to 10 nm.

[0274] A conductive filler layer 125 is formed above the gate electrode 124. The conductive filler layer 125 fills the trench 111 and is electrically connected to a word line (not shown). The conductive filler layer 125 may include, but is not limited to, Ti, TiN, TiON, tungsten, or combinations thereof.

[0275] While the above description illustrates a DRAM device as an example of a semiconductor device, the implementation is not limited thereto and can be applied to all semiconductor devices including oxide films. For example, semiconductor devices can be used for arithmetic operations, program execution, and / or temporary data storage.

[0276] The semiconductor devices used in the implementation can be included in a variety of electronic devices. Electronic devices may include, but are not limited to, mobile devices, computers, laptops, tablet PCs, smartwatches, sensors, digital cameras, e-books, network devices, vehicle navigation systems, Internet of Things (IoT) devices, Internet of Everything (IoE) devices, drones, door locks, safes, ATMs, security devices, medical devices, or vehicle electronic components.

[0277] In implementations, the electronic device may include a memory unit, an arithmetic logic unit, and a control unit, which may be electrically connected to each other. For example, the memory unit, arithmetic logic unit, and control unit may be implemented as a single chip, and may be monolithically integrated onto a single substrate as a single chip. The memory unit, arithmetic logic unit, and control unit may each independently include the aforementioned capacitors and / or semiconductor devices. The electronic device may be connected to one or more input / output devices.

[0278] Specific embodiments are described below. However, the embodiments described below are for illustrative purposes only and are not limited thereto.

[0279] Example

[0280] [1] TGA analysis

[0281] TGA analysis was performed using an Auto-TGA Q500 system (TA Instruments) under a nitrogen atmosphere at a heating rate of 10 degrees Celsius per minute over a temperature range from 30 degrees Celsius to 410 degrees Celsius.

[0282] [2] NMR analysis

[0283] The experiment was performed using FT-NMR (AVANCE III HD 500 MHz) in a benzene-d6 solvent. 1 H NMR analysis.

[0284] Preparation Example 1

[0285] The following reaction scheme was used to synthesize ligand 1 and compound 1:

[0286]

[0287] Synthesis of intermediate L-5

[0288] In a reaction flask, 2-(hydroxymethyl)propane-1,3-diol (18.0 g, 124.0 mmol) was dissolved in tetrahydrofuran (THF, 400 mL), followed by the addition of 4-toluenesulfonic acid monohydrate (1.0 g, 5.2 mmol) and 2,2-dimethoxypropane (23.5 mL, 190.4 mmol). The mixture was stirred at room temperature for approximately 6 hours. After the reaction was complete, the mixture was neutralized with triethylamine (10 mL), followed by removal of volatiles under reduced pressure. The residue was purified by liquid chromatography (HPLC) to obtain intermediate L-5 (19.0 g, 78% yield).

[0289] LC-MS m / z = 147 (M+H) +

[0290] Synthesis of intermediate L-4

[0291] NaH (60% in mineral oil, 4.5 g, 113.0 mmol) was added dropwise to THF (200 mL) in a reaction flask, and intermediate L-5 (15.0 g, 102.6 mmol) dissolved in THF (50 mL) was slowly added at 0°C. After stirring the reaction mixture at room temperature for about 2 hours, benzyl bromide (22.8 g, 133.4 mmol) was added, and the mixture was heated and stirred for 12 hours. After the reaction was complete, water and ethyl acetate were added, and the organic layer obtained from the extraction was dried over magnesium sulfate, followed by removal of volatiles under reduced pressure. The residue was purified by liquid chromatography to obtain intermediate L-4 (23.0 g, 96% yield).

[0292] LC-MS m / z = 237 (M+H) +

[0293] Synthesis of intermediate L-3

[0294] Intermediate L-4 (20.0 g, 84.6 mmol) was dissolved in ethanol (100 mL), and 3N HCl aqueous solution (50 mL) was slowly added dropwise, followed by stirring at room temperature for about 2 hours. After the reaction was complete, the product was obtained under reduced pressure, and the residue was extracted with diethyl ether and purified by liquid chromatography to obtain intermediate L-3 (16.5 g, 99% yield).

[0295] LC-MS m / z = 197 (M+H) +

[0296] Synthesis of intermediate L-2

[0297] NaH (60% in mineral oil, 2.9 g, 73.5 mmol) was added dropwise to THF (100 mL) in a reaction flask, and intermediate L-3 (6.0 g, 30.6 mmol) dissolved in THF (20 mL) was slowly added at 0°C. The reaction mixture was stirred for about 2 hours, followed by the slow addition of methyl iodine (13.0 g, 91.8 mmol), and heating with stirring for 16 hours. After the reaction was complete, water and ethyl acetate were added, and the organic layer obtained from the extraction was dried over magnesium sulfate. The resulting mixture was purified by liquid chromatography to obtain intermediate L-2 (5.7 g, 83% yield).

[0298] LC-MS m / z = 225 (M+H) +

[0299] Synthesis of ligand 1

[0300] In a reaction flask, the synthesized intermediate L-2 (5.5 g, 24.5 mmol) was dissolved in ethanol (60 mL), and Pd / C (10 wt%, 0.6 g) was added. The reaction mixture was purged with H2 gas and stirred at room temperature for one day. After the reaction was complete, the mixture was filtered through diatomaceous earth and purified by liquid chromatography to obtain ligand 1 (3.1 g, 95% yield).

[0301] GC-MS m / z = 135(M+H) +

[0302] 1 H NMR (500MHz, benzene-d6): δ 3.75-3.73 (m, 2H), 3.31 (d, 4H), 3.01 (s, 6H), 2.26 (br s, 1H), 2.05-2.03 (m, 1H).

[0303] Synthesis of Compound 1

[0304] In a reaction flask, bis[bis(trimethylsilyl)amide]strontium (Sr(HMDS)2, purchased from Humist, Yuseon-gu, Daejeon, Korea) (2.0 g, 4.9 mmol) was dissolved in hexane (60 mL). A solution of ligand 1 (1.3 g, 9.8 mmol) in hexane (20 mL) was slowly added dropwise, and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, the mixture was filtered through diatomaceous earth and subjected to fractional distillation under reduced pressure to obtain the strontium compound represented by the following formula (1.2 g, 73% yield). The obtained strontium compound was confirmed to be liquid at room temperature (25°C).

[0305] 1H NMR (500MHz, benzene-d6): δ 4.23 (br s, 2H), 3.77 (br s, 2H), 3.66 (br s, 2H), 3.33 (s, 6H), 2.34 (br s, 1H).

[0306]

[0307] The molecular weights of the prepared strontium compounds were calculated and summarized in Table 1.

[0308] Preparation Example 2

[0309]

[0310] Synthesis of intermediate L2-3

[0311] Intermediate L2-3 (2.5 g, 70% yield) was obtained by the same method as the synthesis of intermediate L-2 in Preparation Example 1, except that methyl iodine was used in a 1 equivalent molar ratio.

[0312] LC-MS m / z = 211 (M+H) +

[0313] Synthesis of intermediate L2-2

[0314] In a reaction flask, NaH (60% in mineral oil, 0.5 g, 12.6 mmol) was added dropwise to THF (60 mL), and intermediate L2-3 (2.2 g, 10.5 mmol) dissolved in THF (10 mL) was slowly added at 0°C. After stirring the reaction mixture for about 2 hours, ethyl iodine (2.5 g, 15.8 mmol) was slowly added, followed by heating and stirring for 12 hours. After the reaction was complete, water and ethyl acetate were added, and the organic layer obtained from the extraction was dried over magnesium sulfate. The resulting mixture was purified by liquid chromatography to obtain intermediate L2-2 (2.0 g, 80% yield).

[0315] LC-MS m / z = 239 (M+H) +

[0316] Synthesis of ligand 2

[0317] Ligand 2 (1.2 g, 95% yield) was synthesized by the same method as ligand 1 in Preparation Example 1, except that intermediate L2-2 was used instead of intermediate L-2.

[0318] GC-MS m / z = 149 (M+H) +

[0319] 1 H NMR (500MHz, benzene-d6): δ 3.76-3.74 (m, 2H), 3.37 (d, 2H), 3.19 (d, 2H), 3.18 (q, 2H), 3.01 (s, 3H), 2.23-2.22 (m, 1H), 2.07-2.05 (m, 1H), 1.00 (t,3H).

[0320] Synthesis of Compound 2

[0321] Compound 2 (0.9 g, 60% yield) was obtained by the same method as in Preparation Example 1, except that ligand 2 was used instead of ligand 1. The obtained strontium compound was confirmed to be liquid at room temperature (25 degrees Celsius).

[0322] 1 H NMR (500MHz, benzene-d6): δ 4.11 (br s, 1H), 4.07 (br s, 1H), 3.65 (br s,3H), 3.57 (br s, 1H), 3.44-3.41 (br m, 2H), 3.27 (s, 3H), 2.27 (br s, 1H),1.17-1.14 (m, 3H).

[0323]

[0324] The molecular weights of the prepared strontium compounds were calculated and summarized in Table 1.

[0325] Preparation Example 3

[0326]

[0327] Synthesis of intermediate L3-2

[0328] Intermediate L3-2 (1.0 g, 78% yield) was synthesized by the same method as intermediate L2-2 in Preparation Example 2, except that propyl iodine was used instead of ethyl iodine.

[0329] GC-MS m / z = 253 (M+H) +

[0330] Synthesis of ligand 3

[0331] Ligand 3 (0.52 g, 80% yield) was synthesized by the same method as ligand 1 in Preparation Example 1, except that intermediate L3-2 was used instead of intermediate L-2.

[0332] GC-MS m / z = 163 (M+H)+

[0333] 1 H NMR (500MHz, benzene-d6): δ 3.77-3.75 (m, 2H), 3.39 (d, 2H), 3.33 (d, 2H), 3.12 (t, 2H), 3.02 (s, 3H), 2.28-2.26 (m, 1H), 2.09-2.04 (m, 1H), 1.42 (q,2H), 0.81 (t, 3H).

[0334] Synthesis of Compound 3

[0335] Compound 3 (1.1 g, 85% yield) was obtained by the same method as in Preparation Example 1, except that ligand 3 was used instead of ligand 1. The obtained strontium compound was confirmed to be liquid at room temperature (25°C).

[0336] 1 H NMR (500MHz, benzene-d6): δ 4.30 (br s, 1H), 4.18 (br s, 1H), 3.86 (br s,2H), 3.79-3.58 (br m, 3H), 3.47 (br s, 4H), 2.37 (br s, 1H), 1.67-1.64 (br m,2H), 0.96 (t, 3H).

[0337]

[0338] The molecular weights of the prepared strontium compounds were calculated and summarized in Table 1.

[0339] Preparation Example 4

[0340]

[0341] Synthesis of intermediate L4-2

[0342] Intermediate L4-2 (0.6 g, 60% yield) was synthesized by the same method as intermediate L-2 in Preparation Example 1, except that propyl iodine was used instead of methyl iodine.

[0343] LC-MS m / z = 281 (M+H) +

[0344] Synthesis of ligand 4

[0345] Ligand 4 (0.37 g, 90% yield) was synthesized by the same method as ligand 1 in Preparation Example 1, except that intermediate L4-2 was used instead of intermediate L-2.

[0346] GC-MS m / z = 192 (M+H) +

[0347] 1 H NMR (500MHz, benzene-d6): δ 3.81-3.79 (m, 2H), 3.44-3.39 (m, 4H), 3.14 (t, 4H), 2.40-2.37 (m, 1H), 2.11-2.09 (m, 1H), 1.47-1.40 (m, 4H), 0.82 (t, 6H).

[0348] Synthesis of Compound 4

[0349] Compound 4 (0.4 g, 83% yield) was obtained by the same method as in Preparation Example 1, except that ligand 4 was used instead of ligand 1. The obtained strontium compound was confirmed to be liquid at room temperature (25°C).

[0350] 1 H NMR (500MHz, benzene-d6): δ 4.27 (br s, 2H), 3.89-3.82 (br m, 4H), 3.57 (br s, 4H), 2.40 (br s, 1H), 1.84-1.74 (br m, 4H), 0.99 (br s, 6H).

[0351]

[0352] The molecular weights of the prepared strontium compounds were calculated and summarized in Table 1.

[0353] Preparation Example 5

[0354]

[0355] Synthesis of ligand 5

[0356] Ligand 5 (0.6 g, 50% yield) was synthesized by the same method as the synthesis of intermediate L-2 and ligand 1 in Preparation Example 1, except that ethyl iodine was used instead of methyl iodine.

[0357] 1H NMR (500MHz, benzene-d6): δ 3.76-3.75 (m, 2H), 3.37 (d, 2H), 3.32 (d, 2H), 3.17 (q, 2H), 3.01 (s, 3H), 2.23 (br s, 1H), 2.07-2.04 (m, 1H), 1.00 (t, 3H).

[0358] Synthesis of Compound 5

[0359] Compound 5 (0.6 g, 75% yield) was obtained by the same method as in Preparation Example 1, except that ligand 5 was used instead of ligand 1. The obtained strontium compound was confirmed to be liquid at room temperature (25°C).

[0360] 1 H NMR (500MHz, benzene-d6): δ 4.13 (br s, 2H), 3.78-3.75 (br m, 4H), 3.56 (br s, 4H), 2.37 (br s, 1H), 1.22 (br s, 6H).

[0361]

[0362] The molecular weights of the prepared strontium compounds were calculated and summarized in Table 1.

[0363] Preparation Example 6

[0364] The following reaction scheme was used to synthesize ligand 7 and compound 7:

[0365]

[0366] Synthesis of ligand 7

[0367] KI (0.2 g, 1 mmol) and K₂CO₃ (41.3 g, 300.0 mmol) were added to a mixture of bis(2-methoxyethyl)amine (13.3 g, 99.8 mmol) and 2-chloroethanol (8.0 g, 99.8 mmol) in a reaction flask, followed by heating and stirring at 80°C for 18 hours. After the reaction was complete, the reaction mixture was purified by liquid chromatography using a mixed solvent of ethyl acetate and ethanol (9:1) to obtain ligand 7 (5.3 g, 30% yield).

[0368] 1 H NMR (500MHz, benzene-d6): δ 3.66 (t, 2H), 3.39 (t, 4H), 3.10 (s, 6H), 2.77-2.75 (m, 6H).

[0369] Synthesis of Compound 7

[0370] Compound 7 (0.8 g, 56% yield) was obtained by the same method as in Preparation Example 1, except that ligand 7 was used instead of ligand 1. The obtained strontium compound was confirmed to be liquid at room temperature (25°C).

[0371] 1 H NMR (500MHz, benzene-d6): δ 4.46-4.26 (br m, 2H), 3.56 (br s, 4H), 3.30 (br s, 6H), 3.17-3.06 (m, 4H), 2.94 (br s, 2H).

[0372] Reference Example 1

[0373] Compounds with the following structures were obtained from STREM Chemicals:

[0374]

[0375] See Example 2

[0376] Synthesize compounds with the following structures according to the following reaction scheme:

[0377]

[0378] Synthesis of Ref. 2

[0379] Ref. 2 was synthesized using the same method as in Preparation Example 1, except that 2-ethylbutanol (purchased from TCI) was used instead of ligand 1. The obtained strontium compound was confirmed to be solid at room temperature (25°C).

[0380] 1 H NMR (500MHz, benzene-d6): δ 3.79 (br s, 2H), 1.63 (br s, 2H), 1.47 (br s, 3H), 1.07 (br s, 6H).

[0381]

[0382] See Example 3

[0383] The following reaction scheme was used to synthesize compound Ref. 3, which has the following structure:

[0384] Synthesis of Ref. 3

[0385]

[0386] Ref. 3 was synthesized using the same method as in Preparation Example 1, except that 1,3-bis(dimethylamino)-2-propanol (purchased from Combi-blocks) was used instead of ligand 1. The obtained strontium compound was confirmed to be in a solid (polymerized) state at room temperature (25°C).

[0387]

[0388] Experimental Example 1

[0389] Thermogravimetric analysis (TGA) was performed on the following: strontium compounds synthesized in Preparation Examples 1 to 6 (Examples 1 to 6), and compounds of Reference Example 1 (Comparative Example 1) and Reference Example 2 (Comparative Example 2).

[0390] Thermogravimetric analysis (TGA) can indicate the volatility of individual compounds. The temperature (T0) of each compound is measured at 10% weight loss. 90% ) and temperature at 50% weight loss (T 50% The results are summarized in Table 1.

[0391] Table 1

[0392]

[0393] Cyclopentadiene-type compounds (Ref. 1, Comparative Example 1), which are conventionally used as strontium precursors, exhibit a Tg exceeding 200°C. 90% and T 50% The value was determined, and the compound was confirmed to be in a solid state. Strontium compounds (Ref. 2, Comparative Example 2) with ligand structures that do not satisfy Formula 1 showed relatively low T values. 90% Value; however, its T 50% A temperature exceeding 400°C indicates very low volatility. Similarly, strontium compounds with ligand structures that do not satisfy Formula 1 (Ref. 3, Comparative Example 3) exhibit relatively low TV. 90% Value, but its T 50% The temperature is approximately 360°C, which also indicates very low volatility.

[0394] It was confirmed that all the strontium compounds in Comparative Examples 1 to 3 were solid at room temperature.

[0395] Conversely, the strontium compounds synthesized in Preparation Examples 1 to 6 exhibited relatively low T values. 90% and T 50% The values ​​indicate that these compounds have improved volatility compared to the comparative examples.

[0396] Furthermore, these results indicate that the strontium compounds synthesized in Preparation Examples 1 to 6 can exhibit high vapor pressure and volatility when applied, for example, in thin film formation processes via vapor deposition.

[0397] While this disclosure has been described in conjunction with embodiments now considered practical, it will be understood that the invention is not limited to the disclosed embodiments. Rather, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

[0398] <Explanation of Symbols>

[0399] 10: First electrode

[0400] 20: Second electrode

[0401] 30: Dielectric film

[0402] 100: Capacitor

[0403] 110: Semiconductor substrate

[0404] 120: Bit Line

[0405] 124: Gate electrode

[0406] 125: Conductive filler layer

[0407] 130: Shallow Trench Isolation (STI)

[0408] 140: Grid insulating film

[0409] 150: Contact

[0410] 160, 180: Interlayer insulating film

[0411] 161, 162: Contacts

[0412] 170: Barrier Layer

[0413] 173: Source Region

[0414] 175: Leakage Zone

[0415] 181, 111: Trench

[0416] 190, 195: Interlayer insulating film

[0417] 200: Transistor

[0418] 500: Semiconductor Devices

Claims

1. Strontium compounds, represented by chemical formula 1: Chemical Formula 1 In chemical formula 1, L1 is the first ligand represented by chemical formula 2. L2 is a second ligand that is different from the first ligand. A is a third ligand that includes oxygen or nitrogen. n is 1 or 2, and m can be 0, 1, 2, 3, or 4. Chemical formula 2 In chemical formula 2, X is nitrogen or CR, where R in CR is hydrogen or a substituted or unsubstituted C1 to C10 alkyl group. * indicates a hydrogen or strontium binding site. n1 is 1 or 2. Each n² is independently 1, 2, or 3. Each Y1 is independently O or NR, wherein R in NR is hydrogen or a substituted or unsubstituted C1 to C10 alkyl group, and R1 and R2 are each independently a substituted or unsubstituted C1 to C5 alkyl group or a Si-containing organic group.

2. The strontium compound according to claim 1, wherein n in chemical formula 1 is 2.

3. The strontium compound according to claim 1, wherein the second ligand comprises a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted acetylacetone group, a substituted or unsubstituted diketone moiety, a substituted or unsubstituted ketimine moiety, a substituted or unsubstituted ketostearate moiety, a substituted or unsubstituted diimine moiety, a carbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted acetoxy group, a substituted or unsubstituted dialkylamino group, a substituted or unsubstituted acetamidine group, a substituted or unsubstituted phenanthroline group, a substituted or unsubstituted dioxime group, a substituted or unsubstituted carbamate group, a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted pyrroleyl group, a substituted or unsubstituted ol group, a substituted or unsubstituted amidine group, a substituted or unsubstituted imidazolyl moiety, a tripyrazolylborate moiety, or a combination thereof.

4. The strontium compound according to claim 1, wherein the first ligand is represented by chemical formula 2-1 or chemical formula 2-2: Chemical formula 2-1 Chemical formula 2-2 ， In chemical formulas 2-1 and 2-2, * indicates a hydrogen or strontium binding site. n1 is 1 or 2. n2 is independently 1 to 3, R is hydrogen or a substituted or unsubstituted C1 to C10 alkyl group, and R1 is a substituted or unsubstituted C1 to C5 alkyl group or a Si-containing organic group, and R2 is a substituted or unsubstituted C1 to C5 alkyl group or a Si-containing organic group, or The first ligand is represented by chemical formula 2-3 or chemical formula 2-4: Chemical formula 2-3 Chemical formula 2-4 In chemical formula 2-3 or chemical formula 2-4 * indicates a hydrogen or strontium binding site. n1 is 1 or 2. n2 is independently 1 to 3, The Rs in CR and NR may be the same or different, and each R is independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group. R1 is a substituted or unsubstituted C1 to C5 alkyl group or a Si-containing organic group, and R2 is a substituted or unsubstituted C1 to C5 alkyl group or an organic group containing Si.

5. The strontium compound according to claim 1, wherein the third ligand comprises a dialkoxyalkane, tetrahydrofuran, pyridine, dialkyl ether, or a combination thereof.

6. The strontium compound according to claim 1, wherein m is 0.

7. The strontium compound according to claim 1, wherein the strontium compound is represented by any one of the following formulas: 。 8. The strontium compound according to claim 1, wherein the strontium compound is in a liquid state at a temperature greater than or equal to 20°C and less than or equal to 50°C.

9. A method for forming an oxide thin film, comprising performing a strontium cycle to obtain a thin film comprising a strontium-containing oxide. The strontium cycle mentioned above includes: A gas containing a strontium precursor is supplied to a process chamber containing a substrate; An inert gas is supplied to the process chamber to purge excess strontium precursor from the process chamber; and The co-reactants are optionally supplied together with the oxidant into the process chamber; Optionally, an inert gas may be supplied to the process chamber to purge excess of the co-reactants and, optionally, the oxidant. The strontium precursor therein comprises a strontium compound according to any one of claims 1 to 8.

10. The method of claim 9, further comprising a first metal cycle, The first metal cycle includes: A gas comprising a first metal precursor is supplied to the process chamber; An inert gas is supplied to the process chamber to purge excess of the first metal precursor; and The reactants used for the reaction with the first metal precursor are supplied to the process chamber. The first metal precursor includes titanium, barium, ruthenium, or a combination thereof.

11. The method of claim 10, wherein the method comprises a plurality of the strontium cycles and a plurality of the first metal cycles.

12. The method of claim 9, wherein the co-reactant comprises water vapor, oxygen, hydrogen, ozone, hydrogen peroxide, or a combination thereof.

13. A method for manufacturing a semiconductor device, comprising: Provides transistors integrated into or disposed on a semiconductor substrate; and Provide a capacitor electrically connected to the transistor. Providing at least one of the transistors or the capacitor includes forming an oxide thin film by the method according to any one of claims 9 to 12.

14. The method of claim 13, wherein providing the capacitor comprises: Provide the first electrode, Forming the oxide thin film, and Provide a second electrode.

15. The method of claim 13, wherein providing the transistor comprises: Trenches are provided in the semiconductor substrate. The oxide film is formed in the trench, and A gate conductor is provided on the oxide thin film.

16. The method of claim 13, wherein the oxide film comprises strontium titanate, lanthanum strontium titanate, barium strontium titanate, or a combination thereof.

17. Semiconductor devices, including: Semiconductor substrate, Transistors integrated in or disposed on the semiconductor substrate, and A capacitor electrically connected to the transistor. At least one of the transistors or the capacitor comprises a thin film comprising a strontium-containing oxide formed by the method according to any one of claims 9 to 12.

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