Strontium compounds, strontium-containing thin films utilizing these compounds, and methods for manufacturing semiconductor devices.

Abstract

This invention provides strontium compounds, strontium-containing thin films utilizing these compounds, and methods for manufacturing semiconductor devices. [Solution] A strontium compound, a thin film deposition method using the same, and a method for manufacturing a semiconductor device, wherein the strontium compound is represented by the following chemical formula. Sr(L1)n(L2) 2-n (A) m In the above chemical formula, n is 1 or 2, L2 is a second ligand different from the first ligand, A is a third ligand containing oxygen or nitrogen, m is 0 to 4, and L1 is the first ligand represented by a predetermined chemical formula.

Description

[Technical Field]

[0001] This invention relates to strontium compounds, strontium-containing thin films, and semiconductor devices that utilize these compounds. [Background technology]

[0002] Strontium or various oxides containing it (e.g., strontium titanate (SrTiO3)) have potential applications as materials in various semiconductor devices or microelectronic devices (e.g., high dielectric constant materials), for example, in the form of nanoscale thin films. Thin films can be formed by various methods, such as CVD and ALD. The development of strontium-containing compounds that can be used for thin film formation is desirable. [Overview of the project] [Problems that the invention aims to solve]

[0003] One object of this embodiment is to provide a compound containing strontium (for example, useful for thin film deposition).

[0004] The object of one embodiment is to provide a compound-based precursor for forming strontium thin films or a composition containing the same.

[0005] The objective of one embodiment is to provide a method for producing a strontium-containing thin film using the compound.

[0006] One embodiment aims to provide a method for manufacturing a semiconductor device using the compound. [Means for solving the problem]

[0007] In one embodiment, the strontium compound is represented by the following chemical formula 1: [ka]

[0008] In Chemical Formula 1, n is 1 or 2, L1 is a first ligand represented by Chemical Formula 2, [Chemical Formula]

[0009] In Chemical Formula 2, X is nitrogen or CR (where R is hydrogen or a substituted or unsubstituted C1-C10 alkyl group), * is a moiety linked to hydrogen or strontium (Sr), n1 is 1 or 2, n2 is, independently of each other, 1 to 3 (for example, 1, 2, or 3), Y1 is, independently of each other and being the same or different, oxygen or NR (where R is hydrogen or a substituted or unsubstituted C1-C10 alkyl group), R1 is a substituted or unsubstituted C1-C5 alkyl group or a Si-containing organic group, R2 is a substituted or unsubstituted C1-C5 alkyl group or a Si-containing organic group, L2 is a second ligand different from the first ligand, A is a third ligand containing oxygen or nitrogen, m is 0 to 4.

[0010] In one embodiment, in the Chemical Formula 1, n can be 2.

[0011] The second ligand may include a substituted or unsubstituted (e.g., C1-C10) alkyl group, a substituted or unsubstituted (e.g., C1-C10) alkoxy group, a substituted or unsubstituted acetylacetonate group, a substituted or unsubstituted β-diketonate residue, a substituted or unsubstituted ketoimine (e.g., β-ketoimine) residue, a substituted or unsubstituted ketostearate (e.g., β-ketostearate) residue, a substituted or unsubstituted diimine (e.g., β-diimine) residue, a substituted or unsubstituted alkyl group, a carbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted acetoxy group, a substituted or unsubstituted dialkylamide group, a substituted or unsubstituted acetamidinato group, a substituted or unsubstituted phenanthroline group, a substituted or unsubstituted glyoximate group, a substituted or unsubstituted carbamate group, a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted alkoxide group, a substituted or unsubstituted amidinato group, a substituted or unsubstituted imidazolyl residue, a tris(pyrazolyl)borate residue, or a mixture thereof.

[0012] The first ligand may be represented by Chemical Formula 2-1 or Chemical Formula 2-2:

Chemical Formula

[0013]

Chemical Formula

[0014] In Chemical Formula 2-1 or Chemical Formula 2-2, * is a moiety linked to hydrogen or strontium, n1 is 1 or 2, n2 is independently 1 to 3 (e.g., 1, 2, or 3), R is hydrogen or a substituted or unsubstituted C1-C10 alkyl group, R1 is a substituted or unsubstituted C1-C5 alkyl group or a Si-containing organic group, R2 is a substituted or unsubstituted C1-C5 alkyl group, or a Si-containing organic group.

[0015] The first ligand may be represented by chemical formula 2-3 or chemical formula 2-4: [ka]

[0016] [ka]

[0017] In chemical formula 2-3 or chemical formula 2-4, * indicates a part that is linked to hydrogen or strontium. n1 is either 1 or 2. n2 can be any of the following independently: 1 to 3, for example, 1, 2, or 3. R is the same or different, each independently of hydrogen or a substituted or unsubstituted C1-C10 alkyl group. R1 is a substituted or unsubstituted C1-C5 alkyl group, or a Si-containing organic group. R2 is a substituted or unsubstituted C1-C5 alkyl group, or a Si-containing organic group.

[0018] The third ligand containing oxygen or nitrogen may or may not include a dialkoxyalkane such as dimethoxyethane, a dialkyl ether such as tetrahydrofuran, pyridine, or diethyl ether, or a combination thereof.

[0019] The strontium compound may or may not contain the dimethoxyethane, THF, pyridine, diethyl ether, or a combination thereof. The strontium compound may or may not contain the third ligand.

[0020] The strontium compound can be represented by one of the following formulas: [ka]

[0021] The strontium compound can be in a liquid state at temperatures of 20°C or higher, and 50°C or lower, or 30°C or lower.

[0022] The strontium compound may have a molecular weight of 150 g / mol or more, 300 g / mol to 1,000 g / mol or less, or 600 g / mol or less.

[0023] The strontium compound, as confirmed by thermogravimetric analysis, has a mass loss of 10% of the total weight of the compound at a temperature (T 90 The %) can be 100°C. The strontium compound is such that, as confirmed by thermogravimetric analysis, the mass loss is 10% of the total weight of the compound at the temperature (T 90 The %) could be 205°C or below, 200°C or below, 190°C or below, 170°C or below, or 150°C or below.

[0024] The strontium compound, as confirmed by thermogravimetric analysis, has a mass loss of 50% of the total weight of the compound at the temperature (T 50 The %) may be 150°C or higher, or 180°C. The strontium compound is determined by thermogravimetric analysis to be at a temperature (T) where the mass loss is 50% of the total weight of the compound. 50 %) may be less than 250°C, 220°C or less, or 200°C or less. In one embodiment, T 50 The percentage can be in the range of 150°C or higher and 220°C or lower, 180°C or higher and 200°C or lower, or a combination of these.

[0025] The strontium compound, as confirmed by thermogravimetric analysis, may exhibit a mass loss of 10% by weight or less, or 8% by weight or less, at temperatures above 250°C and below 400°C, based on the total compound weight.

[0026] In one embodiment, the composition for forming a strontium-containing thin film comprises the strontium compound. The composition may or may not further contain an organic solvent. The organic solvent may be an inert solvent that does not react with the strontium compound.

[0027] The organic solvent may include, for example, substituted or unsubstituted aliphatic hydrocarbon (e.g., alkanes, alkenes, alkynes) solvents, substituted or unsubstituted aromatic hydrocarbon solvents, glyme, polyamine solvents, or combinations thereof.

[0028] In one embodiment, a method for forming an oxide thin film is: The process includes performing a strontium cycle to form a strontium oxide (or to obtain a thin film containing it). The strontium cycle is The step of supplying (e.g., pulsing) a strontium precursor gas to a chamber containing a substrate (e.g., a process chamber); A step of purging excess strontium precursor gas by supplying an inert gas to the chamber (for example, using an inert gas); A step of supplying a co-reactant to the process chamber (for example, by pulsing); and The process includes, by selection, a step of purging excess co-reactant by supplying an inert gas to the chamber (for example, by using an inert gas). The strontium precursor gas comprises a strontium compound according to one embodiment.

[0029] The method described above may further include a first metal cycle for the formation of a first metal oxide.

[0030] The first metal cycle is, A step of supplying a first metal precursor gas to the chamber; A step of purging the excess first metal precursor gas by supplying an inert gas to the chamber (for example, using an inert gas); A step of supplying a first co-reactant for reaction with the first metal precursor to the chamber; and The process includes, by selection, supplying an inert gas to the chamber to purge any excess of the first co-reactant; the first metal precursor may include titanium, barium, ruthenium, or a combination thereof.

[0031] The method described above may include multiple strontium cycles, for example, two or more cycles and up to 500 cycles.

[0032] The method may include multiple first metal cycles, for example, two or more and up to 500 cycles.

[0033] In the method described above, the strontium cycle and the first metal cycle may have a predetermined order or may be repeated alternately.

[0034] The co-reactant may include water vapor, oxygen, ozone, hydrogen peroxide, hydrogen, or a combination thereof.

[0035] The inert gas may include nitrogen gas, argon gas, helium gas, or a combination thereof.

[0036] In one embodiment, a method for manufacturing a semiconductor device includes the steps of providing (for example, forming) a transistor that is integrated on a semiconductor substrate or arranged on the semiconductor substrate, and The step of providing (e.g., forming) a capacitor that is electrically connected to the transistor. Includes, At least one of the steps of providing the transistor and providing the capacitor includes the step of forming the aforementioned oxide thin film.

[0037] The oxide thin film may contain strontium oxide. The oxide thin film or the strontium oxide may further contain a first metal. The first metal may include titanium, barium, ruthenium, or a combination thereof.

[0038] The oxide thin film or the strontium oxide is strontium titanate (SrTiO3), lanthanum strontium titanate, barium strontium titanate [Ba x Sr 1-x The formula may include TiO3 (where 0 ≤ x ≤ 1), or a combination of these.

[0039] The oxide thin film may include a high dielectric constant material.

[0040] The steps of forming the capacitor may include forming a first electrode; forming the oxide thin film; and forming a second electrode.

[0041] The steps of forming the transistor may include forming trenches in the semiconductor substrate, forming the oxide thin film in the trenches, and forming a gate conductor on the oxide thin film.

[0042] In one embodiment, the semiconductor element includes a semiconductor substrate, a transistor integrated on or located on the semiconductor substrate, and a capacitor electrically connected to the transistor. At least one of the transistor and the capacitor includes a strontium-containing oxide thin film (also referred to as a thin film containing strontium oxide) formed by the method described above. [Effects of the Invention]

[0043] One embodiment of the strontium compound can be in a liquid state at a predetermined temperature, for example, room temperature to 50°C, and can exhibit a relatively high vapor pressure. Furthermore, when used in a vapor deposition process (for example, an atomic layer deposition process), the strontium compound can provide process stability and contribute to the mass production of devices containing strontium-containing thin films of a desired composition. [Brief explanation of the drawing]

[0044] [Figure 1] This is a flowchart of the strontium cycle for a method of forming a strontium material (e.g., a strontium-containing oxide thin film) according to one embodiment. [Figure 2] This is a flowchart showing the first metal cycle in a method for forming a strontium material (e.g., a strontium-containing oxide thin film) according to one embodiment. [Figure 3] This is a cross-sectional view of a semiconductor element according to one embodiment. [Figure 4] This is a cross-sectional view of a semiconductor element according to one embodiment. [Modes for carrying out the invention]

[0045] The embodiments are described below in detail so that they can be easily implemented by a person with ordinary skill in the art. However, the structures that are actually applied can be realized in a variety of different forms and are not limited to the embodiments described herein.

[0046] The terms used herein are for illustrative purposes only and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise.

[0047] Here, terms such as “include,” “equip,” or “possess” are intended to specify the existence of the implemented features, figures, stages, components, or combinations thereof, and should be understood not to preemptively exclude the existence or possibility of adding one or more other features, figures, stages, components, or combinations thereof.

[0048] In the drawings, thicknesses are shown enlarged to clearly represent multiple layers and regions, and similar parts are denoted by the same reference numerals throughout the specification. When a layer, film, region, plate, or other part is said to be "on top of" another part, this includes not only when it is "directly above" another part, but also when there is another part in between. Conversely, when one part is said to be "directly above" another part, it means that there is no other part in between.

[0049] In the drawings, unnecessary parts have been omitted to clearly illustrate this embodiment, and the same reference numerals have been used throughout the specification for identical or similar components.

[0050] In the following, "top" or "above" can include not only those directly above, below, to the left, or to the right of a part, but also those above, below, to the left, or to the right of a part that is not in contact with it. Furthermore, when a part "includes" a component, this means that it may include other components, rather than excluding them, unless otherwise specified.

[0051] Here, "these combinations" refers to mixtures, laminates, composites, alloys, blends, etc., of the constituent elements.

[0052] In the following, unless otherwise defined, “substantially,” “approximately,” or “about” means not only the stated value but also the mean within an acceptable range of deviations, taking into account the measurement and the error associated with the measurement of the measured quantity. For example, “substantially” or “approximately” may mean within ±10%, ±5%, ±3%, or ±1% of the stated value or within the standard deviation.

[0053] In the following, unless otherwise defined, "substitution" means that the compound or the residue in question replaces hydrogen with a C1-C30 alkyl group, a C1-C30 alkenyl group, a C2-C30 alkynyl group, a C6-C30 aryl group, a C7-C30 alkylaryl group, a C1-C30 alkoxy group, a C1-C30 heteroalkyl group, a C3-C30 heteroaryl group, a C3-C30 cycloalkyl group, a C3-C15 cycloalkenyl group, a C6-C30 cycloalkynyl group, or a C2 ~C30 heterocycloalkyl groups, halogens (-F, -Cl, -Br, or -I), hydroxyl groups (-OH), nitro groups (-NO2), cyano groups (-CN), amino groups (-NRR', where R and R' are independently hydrogen or C1-C6 alkyl groups), azide groups (-N3), amidino groups (-C(=NH)NH2), hydrazino groups (-NHNH2), hydrazono groups (=N(NH2)), aldehyde groups (-C(=O)H), carbamoyl This means that the group is substituted with substituents selected from -C(O)NH2), thiol groups (-SH), ester groups (-C(=O)OR, where R is a C1-C6 alkyl group or a C6-C12 aryl group), carboxyl groups (-COOH) or their salts (-C(=O)OM, where M is an organic or inorganic cation), sulfonic acid groups (-SO3H) or their salts (-SO3M, where M is an organic or inorganic cation), phosphate groups (-PO3H2) or their salts (-PO3MH or -PO3M2, where M is an organic or inorganic cation), and combinations thereof.

[0054] Here, alkyl refers to a linear or branched saturated monovalent hydrocarbon group (such as methyl or ethylhexyl).

[0055] Here, an alkenyl refers to a linear or branched monovalent hydrocarbon group having one or more carbon-carbon double bonds.

[0056] Here, alkynyl refers to a linear or branched monovalent hydrocarbon group having one or more carbon-carbon triple bonds.

[0057] Here, aryl refers to a group formed by removing one or more hydrogen atoms from an aromatic group (for example, a phenyl or naphthyl group).

[0058] Here, "hetero" refers to the presence of 1 to 3 heteroatoms, which may be N, O, S, Si, P, or combinations thereof.

[0059] Alkoxy refers to an alkyl group (e.g., alkyl-O-) linked via oxygen, such as a methoxy, ethoxy, or sec-butyloxy group.

[0060] One embodiment provides a strontium precursor that can be used in a process (e.g., chemical vapor deposition) for providing Sr-containing thin films (e.g., thin films containing Sr-containing oxides). In one embodiment, the strontium precursor may be a Sr organometallic compound or a Sr coordination compound (e.g., a complex). The strontium precursor of one embodiment can exhibit improved volatility, a relatively low melting point, and relatively high thermal stability, making it a suitable raw material (precursor) for thin film formation in semiconductor manufacturing processes.

[0061] In one embodiment, the strontium compound may be an organometallic complex compound containing strontium and an organic group (e.g., a ligand).

[0062] The strontium compound can be represented by the following chemical formula 1: [ka]

[0063] In chemical formula 1, n is either 1 or 2. L1 is the first ligand, L2 is a second ligand different from the first ligand (e.g., a monoanionic ligand), A is a third ligand containing oxygen or nitrogen, and m is 0 to 4.

[0064] L1 is represented by the following chemical formula 2: [ka]

[0065] In chemical formula 2, X is either nitrogen or -CR- (where R is hydrogen or a substituted or unsubstituted C1-C10 alkyl group, e.g., methyl, ethyl, propyl, isopropyl, or butyl, pentyl, hexyl, etc.). * is the part that is bonded to hydrogen or strontium (Sr). n1 is either 1 or 2. n2 can be any of the following independently: 1 to 3 (for example, 1, 2, or 3). Y1 is either the same or different, independently, oxygen, or NR (where R is hydrogen or a substituted or unsubstituted C1-C10 alkyl group, e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, or isopentyl). R1 is a substituted or unsubstituted C1-C5 alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, or pentyl), or a Si-containing organic group (e.g., a trialkylsilyl group such as Si(CH3)3). R2 is a substituted or unsubstituted C1-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.

[0066] Strontium-containing oxide films can have a perovskite structure exhibiting paraelectric properties. For example, a SrTiO3 thin film deposited by atomic layer deposition (ALD) can achieve a dielectric constant of nearly 150 or higher and can exhibit step coverage of a desired degree of pattern thickness and composition. Therefore, various thin films of Sr-containing materials (e.g., SrTiO3-containing thin films) have potential applications as high-dielectric-constant materials in next-generation DRAM capacitors, for example. Thin film formation can be achieved by various methods, such as sputtering, ion plating, pyrolysis, sol-gel, metal-organic vapor deposition (MOD), and chemical vapor deposition (CVD). ALD (atomic layer deposition) or chemical vapor deposition can be utilized for the manufacture of semiconductor devices due to its compositional controllability, step coverage, mass production potential, and hybrid integration possibilities. While numerous diverse raw materials have been reported as Sr atom sources for chemical vapor deposition, the low volatility, high melting point, and low thermal stability of Sr compounds, which are alkaline earth metals, pose a problem in that the deposition process cannot be operated stably.

[0067] For example, Sr(iPr3Cp)2 (bis(1,2,4-tri-isopropylcyclopentadienyl)strontium) is a relatively widely used strontium precursor. Sr(iPr3Cp)2 can achieve a vapor pressure suitable for deposition by canister heating at around 100 degrees Celsius, but it is highly reactive and there is a risk of initial overgrowth. Above all, Sr(iPr3Cp)2 is in the solid phase at room temperature to 50°C, which can make it difficult to provide the desired level of conformality within high aspect ratio DRAM capacitor structures.

[0068] Conventional technology limits the types of strontium-containing raw materials or precursors that can be used in the vapor deposition process, making it somewhat difficult to carry out the vapor deposition process using them. Most of the strontium precursors available in conventional technology are solid phase with very low vapor pressure. In order for such strontium precursors to provide the desired level of vapor pressure in the process, the canister and line may need to be heated to relatively high temperatures, which may necessitate the use of high-temperature canisters, high-temperature v / v (valve), or a Liquid Delivery System (LDS) method involving solvent dissolution. The inventors have confirmed that conventional strontium precursors have problems with cold spots and contamination due to precursor condensation in the v / v, which can make process or equipment maintenance difficult.

[0069] For example, while a vapor pressure suitable for deposition can be obtained by heating Sr(iPr3Cp)2 in a canister at around 100 degrees Celsius, its high reactivity poses a risk of initial overgrowth. The inventors have confirmed that Sr(iPr3Cp)2 may exist in a solid phase under desired conditions during the deposition process, making it difficult to provide the desired level of conformality within a high-aspect-ratio DRAM capacitor structure. Furthermore, appropriate reactivity of the strontium precursor is desirable in terms of suppressing initial overgrowth and maintaining a low impurity content.

[0070] The molecular size of the strontium precursor needs to be adjusted for step coverage and the possibility of mass production. Therefore, currently, ALD processes using strontium precursors are extremely difficult. Furthermore, from the perspective of mass production, the development of liquid-phase strontium precursors and ALD processes with sufficient vapor pressure is desirable.

[0071] One embodiment of the strontium compound can address these technical problems. This embodiment can exhibit a liquid phase at temperatures of, for example, 20°C to 50°C or 25°C to 35°C (e.g., at room temperature). Furthermore, as confirmed by thermogravimetric analysis, it is expected to provide a desired level of vapor pressure in semiconductor device manufacturing processes (e.g., thin-film deposition or ALD processes).

[0072] In one embodiment, the first ligand may have two or more oxygen atoms, along with oxygen directly bonded to strontium. These oxygen atoms, for example, are added to the oxygen directly bonded to strontium via covalent bonds (when Y1 is oxygen), and can therefore contribute to increased metallic coating by the ligand by interacting with strontium (for example, by interacting with strontium via lone pairs of electrons to form coordinate bonds). In one embodiment, the first ligand may be represented, for example, by chemical formula 2-1 or chemical formula 2-2: [ka]

[0073] [ka]

[0074] In chemical formula 2-1 or chemical formula 2-2, * indicates a part that is linked to hydrogen or strontium. n1 is either 1 or 2. R is hydrogen or a substituted or unsubstituted C1-C10 alkyl group. n2 can be any of the following independently: 1 to 3 (for example, 1, 2, or 3).

[0075] R1 may be a substituted or unsubstituted C1-C5 alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, or isopentyl) or a Si-containing organic group. R2 may be a substituted or unsubstituted C1-C5 alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, or isopentyl) or a Si-containing organic group. When both propyl and isopropyl are mentioned, propyl may mean n-propyl. When both butyl and isobutyl are mentioned, butyl may mean n-butyl. When both pentyl and isopentyl are mentioned, pentyl may mean n-pentyl.

[0076] In a first ligand of this structure, the oxygen atom can be bonded to the strontium atom via a covalent bond or interact by providing a lone pair of electrons (e.g., forming a coordinate bond).

[0077] In one embodiment, the first ligand may contain two, three, or more nitrogen atoms (N in Y1) which can interact with strontium in additional ways (e.g., interact with lone pairs of electrons to form coordinate bonds), contributing to an increase in metallic coating by the ligand. In one embodiment, the first ligand may be represented by chemical formula 2-3 or chemical formula 2-4: [ka]

[0078] [ka]

[0079] In chemical formula 2-3 or chemical formula 2-4, * indicates a part that is linked to hydrogen or strontium. n1 is either 1 or 2. n2 can be any of the following independently: 1 to 3 (for example, 1, 2, or 3). R is the same or different, each independently of hydrogen or a substituted or unsubstituted C1-C10 alkyl group. R1 may be a substituted or unsubstituted C1-C5 alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, or isopentyl) or a Si-containing organic group. R2 may be a substituted or unsubstituted C1-C5 alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, or isopentyl) or a Si-containing organic group.

[0080] With a first ligand of this structure, the nitrogen atom can interact by providing a lone pair of electrons (for example, by forming a coordinate bond).

[0081] In this specification, the Si-containing organic group may be, but is not limited to, a substituted or unsubstituted C1-C10, C2-C3 alkyl group, such as an alkylsilyl group having one or more, two or more, or three methyl, ethyl, or propyl groups, such as a substituted or unsubstituted trimethylsilyl, triethylsilyl, or diethylmethylsilyl group.

[0082] In the above chemical formula, R1 may be the same as or different from R2. The C1-C5 alkyl groups in R1 and R2 may be substituted with halogen groups, amine groups, hydroxyl groups, alkoxy groups, etc., but are not limited to these.

[0083] A strontium compound of one embodiment may contain a first ligand having the structure described herein as the ligand, in the manner described herein. For example, in chemical formula 2 for the first ligand, n1 can provide increased shielding or coverage for strontium by ensuring an appropriate distance between strontium and the first ligand within a defined range, thereby reducing the interaction between the final precursor molecules. In addition, the introduction of a flexible alkyl group in the first ligand of chemical formula 2 can increase entropy, and intermolecular interactions can be minimized in a non-conjugate type. The first ligand of chemical formula 2 contains a lone pair of electrons, which is thought to increase the metal coverage by the ligand and contribute to the stabilization of the strontium atom.

[0084] In the case of strontium precursors using conventional technology, the large size of the strontium atoms leads to frequent intermolecular interactions of the precursor, allowing the molecules to exist in dimer or oligomer form. This can result in an increase in the melting point and viscosity of the precursor compound, as well as a decrease in vapor pressure.

[0085] In one embodiment of the strontium precursor, including the first ligand in the manner described herein can contribute to improving the metal coverage and precursor stability of the ligand and reducing interactions between strontium precursors.

[0086] Therefore, a strontium compound of one embodiment having such a structure can exhibit a liquid state appearance at a predetermined temperature (e.g., room temperature to 50°C) without special treatment. Furthermore, when confirmed by appropriate means such as thermogravimetric analysis, the strontium compound of one embodiment is expected to provide a higher vapor pressure than conventional strontium precursors, for example, under thin-film deposition process conditions. Strontium has a relatively large atomic size. Although not constrained by any particular theory, such a large size of strontium, an alkaline earth metal, can lead to considerable intermolecular interactions between precursors even when ligand coordination is present, which can result in an increased melting point, increased viscosity, and decreased vapor pressure. Therefore, ligands in the conventional art are not well coordinated to allow such strontium atoms to exhibit the desired characteristics.

[0087] In contrast, in the case of a strontium compound of one embodiment, the introduction of the first ligand can reduce the intermolecular interactions of the strontium precursor to a desired level, thereby enabling an increase in the vapor pressure and liquefaction of the precursor. The introduction of the first ligand can result in an increase in the metal(Sr) coverage of the central metal, i.e., strontium, in the precursor.

[0088] In one embodiment, in the chemical formula 1, n may be 2, in which case the strontium compound may contain the first ligand without the second ligand.

[0089] In one embodiment, the strontium compound may have one or more, for example, two, first ligands. In one embodiment, the strontium compound may further contain a second ligand different from the first ligand. The second ligand may be a monoanionic ligand having a different chemical structure from the first ligand. The strontium precursor in one embodiment may not contain the second ligand.

[0090] The second ligand is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted acetylacetonate group, a substituted or unsubstituted β-diketonate residue (e.g., substituted or unsubstituted heptanedione, substituted or unsubstituted acetylacetonate, octanedionate), a substituted or unsubstituted β-ketoiminated residue (e.g., aminopentenonate), a substituted or unsubstituted β-ketostearate residue, a substituted or unsubstituted β-diiminated residue, a substituted or unsubstituted alkyl group, a carbonyl group, a substituted or unsubstituted This may include alkylcarbonyl groups, substituted or unsubstituted acetoxy groups, substituted or unsubstituted dialkylamide groups, substituted or unsubstituted acetamidinate groups, substituted or unsubstituted phenanthroline groups, substituted or unsubstituted glyoximate groups, substituted or unsubstituted carbamate groups, substituted or unsubstituted cyclopentadienyl groups, substituted or unsubstituted pyrrolyl groups, substituted or unsubstituted alkoxide groups, substituted or unsubstituted amidinate groups, substituted or unsubstituted imidazolyl residues, trispirazoleborate residues, or combinations thereof.

[0091] The second ligand can be expressed by the following formula, but is not limited to this: [ka]

[0092] In the above formula, * represents the site that binds to strontium.

[0093] In chemical formula 1, A is a third ligand containing oxygen or nitrogen. This third ligand containing oxygen or nitrogen may be introduced from a solvent used in the synthesis process of the precursor (e.g., a solvent moiety). Such a third ligand may also be removed after synthesis through a removal process.

[0094] In one embodiment, the third ligand may include, but is not limited to, a dialkoxyalkane such as dimethoxyethane; tetrahydrofuran; pyridine; a dialkyl ether such as diethyl ether; or a combination thereof. The strontium compound of one embodiment may further contain or not contain the third ligand. The strontium compound of one embodiment may contain or not contain dimethoxyethane (glyme), THF, pyridine, diethyl ether, or a combination thereof.

[0095] In one embodiment, the strontium compound may be represented by one of the following formulas. [ka]

[0096] The strontium compound of one embodiment can exhibit reduced intermolecular interactions and is in a liquid phase at room temperature, and can therefore be usefully used as a strontium precursor in various deposition processes. The strontium compound can be in a liquid state at temperatures of 20°C or higher and 50°C or lower.

[0097] In one embodiment, the strontium compound may have a temperature of 10% or higher at which it exhibits a 10% weight loss (i.e., the temperature at which the residual weight is 90%), as confirmed by thermogravimetric analysis.

[0098] The strontium compound may have a molecular weight of 150 g / mol or more, 180 g / mol or more, 190 g / mol or more, 200 g / mol or more, 250 g / mol or more, 280 g / mol or more, 300 g / mol or more, 350 g / mol or more, 400 g / mol or more, 410 g / mol or more, 440 g / mol or more, or 450 g / mol. The strontium compound may have a molecular weight of 1,000 g / mol or less, 800 g / mol or less, 600 g / mol or less, 550 g / mol or less, or 500 g / mol or less.

[0099] When the strontium compound is confirmed by thermogravimetric analysis, the temperature (T 90 %) at which the mass (or weight) loss is 10% of the total weight of the compound may be 100 °C or more, 120 °C or more, 130 °C or more, 140 °C or more, or 150 °C. When the strontium compound is confirmed by thermogravimetric analysis, the temperature (T 90 %) at which the mass (or weight) loss is 10% of the total weight of the compound may be 205 °C or less, 200 °C or less, 190 °C or less, 180 °C or less, 170 °C or less, 160 °C or less, or 150 °C.

[0100] When the strontium compound is confirmed by thermogravimetric analysis, the temperature (T 50 %) at which the mass loss is 50% of the total weight of the compound may be 150 °C or more, 160 °C or more, 170 °C or more, 180 °C or more, 185 °C or more, or 190 °C. When the strontium compound is confirmed by thermogravimetric analysis, the temperature (T 50 %) at which the mass loss is 50% of the total weight of the compound may be less than 250 °C, 240 °C or less, 230 °C or less, 220 °C or less, 215 °C or less, 210 °C or less, 205 °C or less, or 200 °C or less.

[0101] When the strontium compound is confirmed by thermogravimetric analysis, the slope defined by the following formula may be -2 or more, -1.7 or more, -1.5 or more, -1.4 or more, -1.3 or more, -1.2 or more, -1.1 or more, and 0 or less or less than 0, or -0.5 or less: Slope = dW / dT (dW = change in weight, dT = change in temperature) Sloe is the weight change per unit of time, and a larger absolute slope value may suggest that the strontium compound vaporizes more effectively.

[0102] When confirmed by thermogravimetric analysis, the strontium compound may exhibit a mass loss of 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0.5% by weight or less, based on the total compound weight.

[0103] While not constrained by any particular theory, one embodiment of the strontium compound may exhibit different thermal behavior from conventional strontium precursors, as confirmed by thermogravimetric analysis, for example. This suggests that the strontium compound of one embodiment may exhibit a relatively reduced vaporization temperature, improved vapor pressure characteristics, and ensure process stability. For example, such a low level of T confirmed by thermogravimetric analysis 50 % and T 90 The percentage may suggest that the strontium compound of one embodiment can exhibit higher volatility and, therefore, an increased vapor pressure.

[0104] A strontium compound of one embodiment can be appropriately synthesized from commercially available reaction reagents using known chemical reactions (for example, by referring to the synthesis method described herein). For example, a strontium compound of one embodiment can be prepared by reacting a first reaction reagent containing a first ligand residue and a reactive group, a second reaction reagent containing a second ligand residue and a reactive group, and a strontium-containing reaction reagent in a suitable solvent. The first or second reaction reagent is commercially available or can be readily obtained by known methods.

[0105] Examples of strontium-containing reaction reagents include, but are not limited to, Sr(HMDS)2 (strontium bis[bis(trimethylsilyl) amide]). Strontium-containing reaction reagents are commercially available or can be easily synthesized by known methods.

[0106] The organic solvent may include, for example, substituted or unsubstituted aliphatic hydrocarbon solvents (e.g., hexane, octane, heptase, etc., alkanes; alkenes; alkynes), substituted or unsubstituted aromatic hydrocarbon solvents such as toluene, ether solvents such as glyme, THF, diethyl ether, pyridine, polyamine solvents, or combinations thereof.

[0107] One embodiment of the strontium compound can exhibit a liquid state at a predetermined temperature (e.g., 20-50°C) and can exhibit an increased level of vapor pressure. Therefore, one embodiment of the strontium compound can be used in the production of thin films through a vapor deposition process (e.g., in the formation of thin films of oxides or high dielectric constant materials during the manufacture of semiconductor devices).

[0108] Therefore, one embodiment relates to a method for manufacturing thin films using the strontium compound.

[0109] In one embodiment, the production of a thin film using a strontium compound may include chemical vapor deposition (CVD) or atomic layer deposition (ALD). Chemical vapor deposition uses a volatile compound, which is vaporized and continuously drawn into the deposition chamber. Such precursor compounds react chemically in the vapor stage or directly on a heated substrate to form a film of the target substance, while unwanted volatile components are removed by reduced pressure or inert gas purging. In the case of CVD, a single-source precursor (SSP) or multiple-source precursors can be used to produce the desired substance. In one embodiment, the strontium compound may be utilized to form a thin film of a material of a desired composition by chemical vapor deposition. Excess precursor or excess co-reactant refers to the portion of reagent remaining in the reaction space after the completion of a self-limiting surface reaction, which may include unreacted gaseous species, weakly physicoadsorbed species, and / or volatile byproducts.

[0110] In one embodiment, the production of a thin film using a strontium compound may include atomic layer deposition technology. In the method of one embodiment, atomic layer deposition technology may involve two alternating surface reactions for thin film formation.

[0111] In atomic layer deposition technology, the substrate surface can be sequentially exposed to a precursor and a reactant, and the two surface reactions can be selectively separated using an inert gas such as argon (Ar) or nitrogen (N2). Once the reaction on the substrate surface is saturated during the precursor (or reactant) exposure stage, no further reaction occurs.

[0112] This self-limiting thin film growth mechanism enables one embodiment of the method, which involves atomic layer deposition technology, to achieve excellent conformality, uniformity, and precise thickness control. In one embodiment of the method, atomic layer deposition technology can be carried out in a cycle manner.

[0113] In one embodiment, a single growth cycle may include the injection of a precursor, substrate exposure of the precursor; purging and draining to remove excess precursor and by-products; injection and exposure of a co-reactant; and purging and draining to remove excess co-reactant and by-products. In atomic layer deposition technology, a defined cycle can be repeated for deposition of the required thickness. Therefore, in atomic layer deposition technology, precise control of the thin film thickness can be achieved by the number of cycles.

[0114] The time required for one cycle can be controlled from a few seconds to a few minutes, and is not particularly limited, depending on (1) the purpose of the process, (2) the chemical properties of the precursor used, (3) the structure of the substrate and the deposition temperature, and (4) the reactivity between the substrate and the precursor. A single cycle can be designed taking into account the geometric characteristics of the substrate to be used, as well as the interaction between the precursor and the co-reactant.

[0115] Therefore, in one embodiment, a method for forming an oxide thin film includes performing a strontium cycle to form a strontium oxide. The strontium cycle is Step (S101) involves supplying a strontium precursor gas to a chamber containing a substrate (e.g., a process chamber) by pulsing (e.g., pulsing); Step (S102) involves supplying an inert gas to the chamber (for example, using an inert gas) to purge the excess strontium precursor gas; and The method includes the step (S103) of supplying a co-reactant to the process chamber (e.g., by pulsing). The strontium precursor gas comprises a strontium compound according to one embodiment. The strontium precursor gas may be a vaporized strontium compound. The strontium precursor gas may or may not contain an inert gas as a carrier gas. The method may further include the step (S104) of purging excess co-reactant by supplying an inert gas to the process chamber (e.g., using an inert gas). (See Figure 1) The supply of the strontium precursor gas can be carried out by an appropriate method and is not particularly limited. The supply of the strontium precursor gas may include the use of a thin film manufacturing composition. In one embodiment, the thin film manufacturing composition comprises the strontium compound. The composition may or may not further contain an organic solvent. The organic solvent may be an inert solvent that does not react with the strontium compound. The organic solvent is not particularly limited, and any of the solvents listed above may be used as the reaction solvent. In one embodiment, the organic solvent may include, but is not limited to, toluene, hexane, octane, and the like.

[0116] The supply of strontium precursor gas may involve heating or reducing the pressure of the thin-film manufacturing composition in a container in which the thin-film manufacturing composition is stored to vaporize it into vapor, which is then supplied to the chamber on which the substrate is placed. In one embodiment, the thin-film manufacturing composition may be supplied in a liquid state to a vaporization chamber, where it is heated or reduced the pressure to vaporize it into vapor, which is then supplied to the chamber on which the substrate is placed.

[0117] The supply of the strontium precursor gas can be carried out with the assistance of a carrier gas. For example, the liquid-phase precursor can be vaporized by bubbling the carrier gas while selectively heating it. The strontium compound (i.e., the strontium precursor) in one embodiment is in a liquid state under the conditions of the method in one embodiment, which is advantageous for vaporization. The carrier gas can be appropriately selected. The carrier gas can include inert gases such as nitrogen, argon, and helium.

[0118] The strontium precursor supplied into the chamber can react with and be adsorbed by the substrate. All reactive sites on the substrate are adsorbed by the strontium precursor, and any remaining excess strontium precursor and by-products can be removed in the subsequent purging step (S102).

[0119] Next, a co-reactant can be supplied to the process chamber (e.g., by pulsing). The co-reactant reacts with a strontium precursor adsorbed on the substrate to form a thin film of strontium-containing material (e.g., strontium oxide). In some embodiments, including plasma enhancement, the co-reactant may be plasma-ignited.

[0120] The reaction with the co-reactant may consume all reactive sites on the substrate surface, at which point the chamber can be purged again using an inert carrier gas (S104). Next, it is determined whether the thin film formed on the substrate has reached the desired thickness or composition. If it has not reached the desired thickness or composition, the strontium cycle can be repeated until the film formed on the substrate reaches the desired thickness.

[0121] The method may further include a first metallic cycle for the formation of a first metal oxide. The first metallic cycle is Step (S201): Supplying the first metal precursor gas to the aforementioned process chamber; Step (S202) involves supplying an inert gas to the process chamber (for example, using an inert gas) to purge the excess first metal precursor gas; and The process includes the step (S203) of supplying a first co-reactant to the process chamber for reaction with the first metal precursor. The first metal cycle may further include the step (S204) of supplying an inert gas to the process chamber to purge any excess of the first co-reactant. The first metal precursor may include titanium, barium, ruthenium, or a combination thereof.

[0122] The type of first metal precursor is not particularly limited and can be appropriately selected. The first metal precursor includes, but is not limited to, metal alkoxides and organometallic ammonium salts. If the first metal precursor contains titanium, it may include, but is not limited to, titanium compounds such as Ti(OiPr)4, Ti(OtBu)4, Ti(NMe2)4, Ti(NEtMe)4, and Ti(NEt2)4. Here, iPr means isopropyl, tBu means t-butyl, Me means methyl, and Et means ethyl.

[0123] For gas preparation and supply of the first metal precursor, refer to the description for the strontium precursor.

[0124] The method may include multiple strontium cycles. The method may also include multiple first metallic cycles. In the method, the strontium cycles and the first metallic cycles may have a predetermined order, taking into account the composition of the thin film to be formed, or they may be repeated alternately, but the order is not particularly limited.

[0125] One embodiment of the strontium compound and the thin film formation method using the same can be utilized in the manufacture of semiconductor devices (e.g., capacitors or transistors) (e.g., for the formation of dielectric films or insulating films).

[0126] Therefore, in one embodiment, a method for manufacturing a semiconductor device includes the steps of providing (for example, forming) a transistor that is integrated on a semiconductor substrate or arranged on the semiconductor substrate, and The step of providing (e.g., forming) a capacitor that is electrically connected to the transistor. Includes, At least one of the steps of forming the transistor and forming the capacitor includes the step of forming the aforementioned thin film (for example, a strontium material-containing thin film or a strontium oxide-containing thin film).

[0127] The oxide thin film may contain strontium oxide. The oxide thin film or the strontium oxide may further contain a first metal. The first metal may include titanium, barium, ruthenium, or a combination thereof.

[0128] The oxide thin film or the strontium oxide is strontium titanate (SrTiO3), lanthanum strontium titanate, barium strontium titanate [Ba x Sr 1-x The formula may include TiO3 (where 0 ≤ x ≤ 1), or a combination of these.

[0129] The oxide thin film may include a high dielectric constant material.

[0130] In one embodiment of a semiconductor device manufacturing method, the step of forming the capacitor may include the steps of forming a first electrode; forming the oxide thin film; and forming a second electrode. The oxide thin film (or dielectric film) may be formed by a thin film formation method described herein. The capacitor may be formed along the profile of the first electrode. The formation of the capacitor dielectric film can be shown with reference to the flowcharts in Figures 1 and 2. A second electrode may be formed on the formed capacitor dielectric film. The methods for forming the first and second electrodes are not particularly limited and can be appropriately selected.

[0131] In one embodiment, the steps of forming the transistor may include forming a trench in the semiconductor substrate, forming the oxide thin film in the trench, and forming a gate conductor on the oxide thin film. The formation of the oxide thin film (or gate insulating film) may be carried out by the thin film formation methods described herein (for example, the flowcharts in Figures 1 and 2).

[0132] In one embodiment, the semiconductor element is a semiconductor substrate, A transistor integrated on the semiconductor substrate or located on the semiconductor substrate, and This includes a capacitor electrically connected to the transistor.

[0133] At least one of the transistor and the capacitor includes a strontium-containing oxide thin film (formed, for example, by the method described above). The aforementioned oxide film can be applied as a dielectric layer, insulating layer, passivation layer and / or protective layer of various devices. The devices may be, for example, semiconductor devices or display devices.

[0134] Hereinafter, an example of a semiconductor device according to one embodiment will be described with reference to the drawings.

[0135] Figure 3 is a cross-sectional view showing an example of a semiconductor device according to one embodiment.

[0136] Referring to Figure 3, a semiconductor element 500 according to one embodiment includes a semiconductor substrate 110, a transistor 200, and a capacitor 100. At least one of the transistor 200 and the capacitor 100 may include an oxide film, which can be formed by the method described above. The oxide film may be, for example, a strontium oxide film.

[0137] The semiconductor substrate 110 may include silicon; germanium; silicon-germanium; III-V group compounds such as GaP, GaAs, and GaSb; or combinations thereof. For example, the semiconductor substrate 110 may be a silicon-on-insulator (SOI) substrate or a germanium-on-insulator (GOI) substrate.

[0138] The transistor 200 can be located in an active region defined by a shallow trench isolation (STI) 130 within the semiconductor substrate 110, and can be electrically coupled to the bit line 120 and the capacitor 100 to perform a switching function. The transistor 200 may be a field-effect transistor (FET) including a source region 173, a drain region 175, a gate electrode 124, and a gate insulating film 140. Field-effect transistors (FETs) can have a variety of structures, and may be, but are not limited to, FinFETs, GAAFETs, MBCFETs, CFETs, or VFETs.

[0139] The source region 173 and the drain region 175 are provided on the semiconductor substrate 110 and are spaced apart along the in-plane direction of the semiconductor substrate 110. The source region 173 and the drain region 175 may be conductive regions of the semiconductor substrate 110 that are highly doped with p-type or n-type impurities. In the case of an n-type transistor, the source region 173 and the drain region 175 are highly doped with n-type impurities, and in the case of a p-type transistor, the source region 173 and the drain region 175 may be highly doped with p-type impurities. The source region 173 is electrically connected to the capacitor 100, and the drain region 175 may be electrically connected to the bit line 120.

[0140] The gate electrode 124 is formed on the semiconductor substrate 110 and can be located between the source region 173 and the drain region 175. The gate electrode 124 may include, but is not limited to, a low-resistance conductor, such as Ti, TiN, TiON, or a combination thereof. The gate electrode 124 may be formed in one or more layers.

[0141] The gate insulating film 140 is located between the gate electrode 124 and the semiconductor substrate 110 and may include the oxide film described above. The gate insulating film 140 may include an oxide film formed by the atomic layer deposition described above, and may be, for example, a strontium oxide film. A specific explanation of the strontium oxide film is as described above.

[0142] Interlayer insulating films 160 and 180 are formed on the transistor 200. The interlayer insulating films 160 and 180 may include, but are not limited to, oxides, nitrides, oxynitrides, or combinations thereof, including, for example, silicon, aluminum, hafnium, lanthanum, zirconium, tantalum, yttrium, titanium, barium, strontium, or alloys thereof. The interlayer insulating films 160 and 180 have a plurality of contact holes, which are filled with a conductor to form a plurality of contacts 161, 162, and 150.

[0143] A bit line 120 is formed between the interlayer insulating films 160 and 180. The bit line 120 is electrically connected to the drain region 175 of the transistor 200 via a contact 162. The bit line 120 is positioned to intersect with a word line (not shown), and the bit line 120 and the word line can form multiple arrays. The word line can be electrically connected to the gate electrode 124.

[0144] The capacitor 100 is embedded within the interlayer insulating film 180, specifically within a trench 181 formed in the interlayer insulating film 180. The shape of the trench 181 is not particularly limited; for example, the connection between the bottom and sides of the trench 181 may be rounded, or the sides of the trench 181 may be inclined at a predetermined angle. The trench 181 can have a high aspect ratio, and the higher the aspect ratio, the higher the capacitance of the capacitor 100. The capacitor 100 is electrically connected to the source region 173 of the transistor 200 through a contact 161.

[0145] The capacitor 100 includes a first electrode 10, a dielectric film 30, and a second electrode 20.

[0146] The first electrode 10 is located within the trench 181 along the inner wall of the interlayer insulating film 180. The first electrode 10 may be a thin film, for example, a continuous thin film formed to a substantially uniform thickness along the inner wall of the interlayer insulating film 180 within the trench 181. For example, the first electrode 10 may be formed by atomic layer deposition (ALD).

[0147] The dielectric film 30 may include a thin film (e.g., an oxide thin film or a strontium oxide thin film) formed by a thin film formation method described herein (e.g., atomic layer deposition). The oxide thin film or the strontium oxide thin film may be strontium titanate (SrTiO3), lanthanum strontium titanate, barium strontium titanate [Ba x Sr 1-x The formula may include TiO3 (where 0 ≤ x ≤ 1), or a combination of these.

[0148] The dielectric film 30 is located on the first electrode 10 along the inner wall of the interlayer insulating film 180 within the trench 181 and may be a continuous thin film formed to a substantially uniform thickness along the inner wall of the interlayer insulating film 180 within the trench 181. The thickness of the dielectric film 30 may be about 1 nm to 100 nm, and within that range may be about 2 nm to 80 nm, about 2 nm to 50 nm, or about 2 nm to 30 nm.

[0149] The second electrode 20 can fill the interior of the trench 181. However, it is not limited to this, and the second electrode 20 may fill a portion of the trench 181 and then be filled with a filler material. The second electrode 20 can include, for example, a metal, a metal nitride, a metal oxynitride, or a combination thereof, and may include, but is not limited to, Ti, TiN, TiON, TaN, MoN, CoN, TiAlN, TaAlN, W, Ru, Ir, IrO2, Pt, or a combination thereof.

[0150] The contact 150 can be located within the interlayer insulating film 180, and the bit line 120 and the upper wiring can be electrically connected through the contact 150. A barrier layer 170 may be formed around the contact 150.

[0151] One or more layers of interlayer insulating films 190, 195 are located on top of the capacitor 100, and the capacitor 100 can be electrically connected to wiring (not shown) embedded within the interlayer insulating films 190, 195.

[0152] Figure 4 is a cross-sectional view showing another example of a semiconductor device according to one embodiment.

[0153] Referring to Figure 4, a semiconductor element 500 according to one embodiment includes a semiconductor substrate 110, a transistor 200, and a capacitor 100, similar to the example described above. At least one of the transistor 200 and the capacitor 100 may be a thin film (e.g., an oxide thin film or a strontium oxide thin film) formed by a thin film formation method described herein (e.g., atomic layer deposition). The oxide thin film or the strontium oxide thin film may be strontium titanate (SrTiO3), lanthanum strontium titanate, barium strontium titanate [Ba x This may include SrTiO3 (where 0 ≤ x ≤ 1), or a combination thereof.

[0154] In this example, the semiconductor element 500 may include, but is not limited to, a transistor 200 with a BCAT (buried cell array transistor) structure in which the gate electrode 124 and gate insulating film 140 are embedded within the semiconductor substrate 110.

[0155] The transistor 200 has a plurality of trenches 111. The trenches 111 are formed to a predetermined depth from the surface of the semiconductor substrate 110, and the inner wall of the semiconductor substrate 110 can be exposed. The shape of the trenches 111 is not particularly limited; for example, the connecting portion between the bottom and side of the trench 111 may be rounded, or the side of the trench 111 may be inclined at a predetermined angle.

[0156] The gate insulating film 140 is located along the inner wall of the semiconductor substrate 110 within the trench 111. The gate insulating film 140 may include the aforementioned thin films, for example, a strontium-containing oxide thin film. The oxide thin film or the strontium oxide thin film may be strontium titanate (SrTiO3), lanthanum strontium titanate, barium strontium titanate [ BaxSr1-x The gate insulating film 140 may include TiO3 (wherein 0 ≤ x ≤ 1) or a combination thereof. The gate insulating film 140 may be a continuous thin film formed to a substantially uniform thickness along the inner wall of the semiconductor substrate 110 in the trench 111 by, for example, the atomic layer deposition method described above. The thickness of the gate insulating film 140 may be, for example, about 1 nm to 30 nm, and within that range, it may be about 3 nm to 20 nm or about 5 nm to 10 nm.

[0157] The gate electrode 124 can fill a portion of the trench 111. However, it is not limited to this, and the gate electrode 124 may be a continuous thin film located on the gate insulating film 140 along the inner wall of the semiconductor substrate 110 within the trench 111. The gate electrode 124 may include a low-resistance conductor, such as Ti, TiN, TiON, or a combination thereof. The thickness of the gate electrode 124 may be, for example, about 1 nm to 30 nm, and within that range, it may be about 3 nm to 20 nm or about 5 nm to 10 nm.

[0158] A filler conductive layer 125 is formed on the gate electrode 124. The filler conductive layer 125 fills the trench 111 and can be electrically connected to a word line (not shown). The filler conductive layer 125 may, but is not limited to, Ti, TiN, TiON, tungsten, or a combination thereof.

[0159] Although the above explanation used DRAM elements as an example of semiconductor elements, it is not limited to this and can be applied to all semiconductor elements, including oxide films. For example, semiconductor elements can be used for arithmetic operations, program execution, and / or temporary data storage.

[0160] The aforementioned semiconductor elements can be included in a wide variety of electronic devices. These electronic devices may include, but are not limited to, mobile devices, computers, laptops, tablet PCs, smartwatches, sensors, digital cameras, e-readers, network devices, vehicle navigation systems, the Internet of Things (IoT), Internet of Everything (IoE), drones, door locks, safes, automated teller machines (ATMs), security devices, medical devices, or automotive electrical components.

[0161] As an example, an electronic device may include a memory unit, an arithmetic logic unit, and a control unit, which may be electrically connected. For example, the memory unit, arithmetic logic unit, and control unit may be implemented on a single chip, for example, monolithically integrated on a single substrate. Each of the memory unit, arithmetic logic unit, and control unit may independently include the aforementioned capacitors and / or semiconductor elements. The electronic device may be connected to one or more input / output devices.

[0162] The embodiments described above will be explained in more detail below through the examples. However, the following examples are for illustrative purposes only and do not limit the scope of rights.

[0163] [Examples] Analysis method [1]TGA analysis The experiment was conducted at a heating rate of 10°C / min at temperatures ranging from 30°C to 400°C, under nitrogen gas conditions, using an Auto-TGA Q500 system (TAI Instruments).

[0164] [2] NMR analysis 1H NMR analysis was performed using FT-NMR (AVANCE III HD 500MHz) in benzene-d6 solvent.

[0165] Synthesis Example 1 Ligand 1 and compound 1 were synthesized according to the following reaction scheme: [ka]

[0166] Synthesis of intermediate L-5 18.0 g (124.0 mmol) of 2-(Hydroxymethyl)propane-1,3-diol was dissolved in 400 ml of tetrahydrofuran (THF), and 1.0 g (5.2 mmol) of 4-toluenesulfonic acid monohydrate and 23.5 mL (190.4 mmol) of 2,2-dimethoxypropane were added. The mixture was then stirred at room temperature for approximately 6 hours. After the reaction was complete, the mixture was neutralized with triethylamine (10 mL), and the resulting product was distilled under reduced pressure. The product was then purified by liquid chromatography to obtain intermediate L-5, 19.0 g (78% yield). LC-MSm / z=147(M+H)+ Synthesis of intermediate L-4 4.5 g (113.0 mmol) of NaH (60% in mineral oil) was added to 200 ml of THF, and then 15.0 g (102.6 mmol) of intermediate L-5, dissolved in 50 ml of THF at 0°C, was slowly added. The reaction mixture was stirred at room temperature for about 2 hours, then 22.8 g (133.4 mmol) of benzyl bromide was added and the mixture was heated and stirred for 12 hours. Water and ethyl acetate were added to the resulting product, and the extracted organic layer was dried over magnesium sulfate. After vacuum distillation, the mixture was purified by liquid chromatography to obtain 23.0 g (96% yield) of intermediate L-4. LC-MSm / z=237(M+H)+ Synthesis of intermediate L-3 Intermediate L-4 (20.0 g, 84.6 mmol) was dissolved in 100 ml of ethanol, and then 3N HCl aqueous solution (50 ml) was slowly added dropwise while stirring at room temperature for about 2 hours. After the reaction was complete, the resulting product was distilled under reduced pressure, and the resulting residue was extracted with diethyl ether and purified by liquid chromatography to obtain intermediate L-3 (16.5 g, 99% yield). LC-MSm / z=197(M+H)+ Synthesis of intermediate L-2 2.9 g (73.5 mmol) of NaH (60% in mineral oil) was added to 100 ml of THF, and then 6.0 g (30.6 mmol) of intermediate L-3, dissolved in 20 ml of THF at 0°C, was slowly added. After stirring the reaction mixture for about 2 hours, 13.0 g (91.8 mmol) of methyl iodide was slowly added and the mixture was heated and stirred for 16 hours. Water and ethyl acetate were added to the resulting product for extraction, and the organic layer was dried over magnesium sulfate. The resulting mixture was purified by liquid chromatography to obtain 5.7 g (83% yield) of intermediate L-2. LC-MSm / z=225(M+H)+ Synthesis of Ligand-1 5.5 g (24.5 mmol) of the synthesized intermediate L-2 was dissolved in 60 ml of ethanol, and then 0.6 g of Pd / C at 10% by weight 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 Celite, and the resulting mixture was purified by liquid chromatography to obtain 3.1 g of Ligand-1 (95% yield). GC-MSm / z=135(M+H)+ 1H NMR (500MHz, benzene-d6): δ3.75-3.73(m, 2H), 3.31(d, 4H), 3.01(s, 6H), 2.26(br s, 1H), 2.05-2.03(m, 1H) Synthesis of Compound 1 2.0 g (4.9 mmol) of strontium bis[bis(trimethylsilyl) amide] (Sr(HMDS)2, purchased from Humist, 55-1, Techno 11-ro, Yuseong-gu, Daejeon) was dissolved in 60 ml of hexane. Then, 1.3 g (9.8 mmol) of Ligand 1 dissolved in 20 ml of hexane was slowly added dropwise, and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, the mixture was filtered using Celite, and fractional distillation was performed under reduced pressure to obtain 1.2 g (73% yield) of the strontium compound represented by the following formula. The prepared strontium compound was confirmed to be in liquid state at room temperature (25°C). 1H NMR (500MHz, benzene-d6): δ4.23 (br s, 2H), 3.77 (br s, 2H), 3.66 (br s, 2H), 3.33 (s, 6H), 2.34 (br s, 1H) [ka]

[0167] The molecular weights of the manufactured strontium compounds were calculated and summarized in Table 1.

[0168] Synthesis Example 2 [ka]

[0169] Synthesis of intermediate L2-3 Except for using 1 equivalent of methyl iodide relative to the number of moles, 2.5 g of intermediate L2-3 was obtained using the same method as the synthesis method for intermediate L-2 in Synthesis Example 1 (yield 70%). LC-MSm / z=211(M+H)+ Synthesis of intermediate L2-2 0.5 g (12.6 mmol) of NaH (60% in mineral oil) was added to 60 ml of THF, and then 2.2 g (10.5 mmol) of intermediate L2-3, dissolved in 10 ml of THF at 0°C, was slowly added. The reaction mixture was stirred for approximately 2 hours, and then 2.5 g (15.8 mmol) of ethyl iodide was slowly added and the mixture was heated and stirred for 12 hours. Water and ethyl acetate were added to the resulting product for extraction, and the organic layer was dried over magnesium sulfate. The resulting mixture was purified by liquid chromatography to obtain 2.0 g (80% yield) of intermediate L2-2. LC-MSm / z=239(M+H)+ Synthesis of Ligand-2 Ligand-2 1.2g (95% yield) was synthesized using the same method as the synthesis method for intermediate Ligand-1 in Synthesis Example 1, except that intermediate L2-2 was used instead of intermediate L-2. GC - MSm / z = 149(M+H)+ 1H NMR (500MHz, benzene-d6): δ3.76-3.74(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) Synthesis of Compound 2 Compound 2 was obtained in 0.9 g (60% yield) using the same method as in Synthesis Example 1, except that Ligand-2 was used instead of Ligand-1. The prepared strontium compound was confirmed to be in liquid state at room temperature (25°C). 1H NMR (500MHz, benzene-d6): δ4.11(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) [ka]

[0170] The molecular weights of the manufactured strontium compounds were calculated and summarized in Table 1.

[0171] Synthesis Example 3 [ka]

[0172] Synthesis of intermediate L3-2 Intermediate L3-2 was synthesized in 1.0 g (78% yield) using the same method as the synthesis of intermediate L2-2 in Synthesis Example 2, except that propyl iodide was used instead of ethyl iodide. GC-MSm / z=253(M+H)+ Synthesis of Ligand-3 Ligand-3 0.52 g (80% yield) was synthesized using the same method as the synthesis method for intermediate Ligand-1 in Synthesis Example 1, except that intermediate L3-2 was used instead of intermediate L-2. GC - MSm / z = 163(M+H) + 1H NMR (500MHz, benzene-d6): δ3.77-3.75(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) Synthesis of Compound 3 Compound 3 was obtained in 1.1 g (85% yield) using the same method as in Synthesis Example 1, except that Ligand-3 was used instead of Ligand-1. The prepared strontium compound was confirmed to be in liquid state at room temperature (25°C). 1H NMR (500MHz, benzene-d6): δ4.30(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) [ka]

[0173] The molecular weights of the manufactured strontium compounds were calculated and summarized in Table 1.

[0174] Synthesis Example 4 [ka]

[0175] Synthesis of intermediate L4-2 Intermediate L4-2 0.6g (yield 60%) was synthesized using the same method as the synthesis method for intermediate L-2 in Synthesis Example 1, except that propyl iodide was used instead of methyl iodide. LC-MSm / z=281(M+H)+ Synthesis of Ligand-4 Ligand-4 0.37 g (90% yield) was synthesized using the same method as the synthesis method for intermediate Ligand-1 in Synthesis Example 1, except that intermediate L4-2 was used instead of intermediate L-2. GC - MSm / z = 192(M+H) + 1H NMR (500MHz, benzene-d6): δ3.81-3.79(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) Synthesis of Compound 4 Compound 4 was obtained in 0.4 g (83% yield) using the same method as in Synthesis Example 1, except that Ligand-4 was used instead of Ligand-1. The prepared strontium compound was confirmed to be in liquid state at room temperature (25°C). 1H NMR (500MHz, benzene-d6): δ4.27(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) [ka]

[0176] The molecular weights of the manufactured strontium compounds were calculated and summarized in Table 1.

[0177] Synthesis Example 5 [ka]

[0178] Ligand5 synthesis Ligand-5 0.6 g (50% yield) was synthesized using the same method as the synthesis of intermediate L-2 and Ligand-1 in Synthesis Example 1, except that ethyl iodide was used instead of methyl iodide. 1H NMR (500MHz, benzene-d6): δ3.76-3.75(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) Synthesis of Compound 5 Compound 5 was obtained in 0.6 g (75% yield) using the same method as in Synthesis Example 1, except that Ligand-5 was used instead of Ligand-1. The prepared strontium compound was confirmed to be in liquid state at room temperature (25°C). 1H NMR (500MHz, benzene-d6): δ4.13 (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) [ka]

[0179] The molecular weights of the manufactured strontium compounds were calculated and summarized in Table 1.

[0180] Synthesis Example 6 Ligand7 and compound 7 were synthesized according to the following reaction scheme: [ka]

[0181] Ligand7 synthesis A mixture of 13.3 g (99.8 mmol) of bis(2-methoxyethyl)amine and 8.0 g (99.8 mmol) of 2-chloroethanol was mixed with 0.2 g (1.0 mol%) of KI and 1.3 g (300.0 mmol) of K2CO3, and the mixture was heated and stirred at 80°C for 18 hours. After the reaction was complete, the reaction mixture was purified by liquid chromatography using a 9:1 mixture of ethyl acetate and ethanol to obtain 5.3 g of Ligand7 (30% yield). 1H NMR (500MHz, benzene-d6): δ3.66(t, 2H), 3.39(t, 4H), 3.10(s, 6H), 2.77-2.75(m, 6H) Synthesis of Compound 7 Compound 7 was obtained in 0.8 g (56% yield) using the same method as in Synthesis Example 1, except that Ligand-7 was used instead of Ligand-1. The prepared strontium compound was confirmed to be in liquid state at room temperature (25°C). 1H NMR (500MHz, benzene-d6): δ4.46-4.26(br m, 2H), 3.56(br s, 4H), 3.30(br s, 6H), 3.17-3.06(m, 4H), 2.94(br s, 2H) Reference Example 1 The compound with the following structure was obtained from STREM Chemicals: [Chemical formula]

[0182] Reference Example 2 The compound with the following structure was synthesized according to the following reaction scheme: [Chemical formula]

[0183] Synthesis of Ref2. Ref2. was synthesized using a method similar to that of Synthesis Example 1, except that 2-ethylbutyl alcohol (purchased from TCI) was used instead of Ligand-1. The strontium compound produced was confirmed to be in a solid state at room temperature (25°C). 1H NMR (500 MHz, benzene-d6): δ 3.79 (br s, 2H), 1.63 (br s, 2H), 1.47 (br s, 3H), 1.07 (br s, 6H) [Chemical formula]

[0184] Reference Example 3 Compound Ref. 3 with the following structure was synthesized according to the following reaction scheme: Synthesis of Ref3. [Chemical formula]

[0185] Ref. 3 was synthesized using the same method as in Synthesis Example 1, except that 1,3-bis(dimethylamino)-2-propanol (purchased from Combi-blocks) was used instead of Ligand-1. The produced strontium compound was confirmed to be in a solid (polymeric) state at room temperature (25°C). [ka]

[0186] Experimental Example 1 Thermogravimetric analysis was performed on the strontium compounds synthesized in Synthesis Examples 1-6 (Examples 1-6), as well as the compound from Reference Example 1 (Comparative Example 1) and the compound from Reference Example 2 (Comparative Example 2).

[0187] Thermogravimetric analysis can suggest the volatility of each compound. Temperature at 10% weight loss (T 90 %) and temperature T at a weight reduction of 50% 50 The percentages were measured for each component, and the results are summarized in Table 1.

[0188] [Table 1]

[0189] The cyclopentadiene type compounds (ref. 1, Comparative Example 1) used as strontium precursors in conventional technology are conditioned at temperatures above 200°C. 90 % and T 50 It showed a percentage, and we were able to confirm that the compound was in a solid state. Strontium compounds having ligands with a structure that does not satisfy chemical formula 1 (ref. 2, Comparative Example 2) 90 The percentage is at a low level, 50 It was found that the % volatility was very low above 400°C. Strontium compounds having ligands with a structure that does not satisfy chemical formula 1 (ref. 3, Comparative Example 3) 90 The percentage is at a low level, 50It was found that the % has very low volatility at around 360°C.

[0190] It was confirmed that all of the strontium compounds of Comparative Examples 1 to 3 are solids at room temperature.

[0191] In contrast to this, the strontium compounds synthesized in Synthesis Examples 1 to 6 show a relatively low level of T 90 % and T 50 %, and such results suggest that these compounds exhibit improved volatility compared to the comparative examples.

[0192] Also, from such results, it was found that the strontium compounds synthesized in Synthesis Examples 1 to 6 can exhibit a high vapor pressure and volatility when applied to, for example, a thin film formation method by vapor deposition.

[0193] Although the embodiments of the present invention have been described in detail above, the scope of the rights of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention defined in the following claims also belong to the scope of the rights of the present invention.

Explanation of Reference Numerals

[0194] 10: First electrode 20: Second electrode <l 30: Dielectric film 100: Capacitor 110: Semiconductor substrate 120: Bit line 124: Gate electrode 125: Interlayer conductive layer 130: Shallow trench isolation (STI) 140: Gate insulating film 150: Contact 160, 180: Interlayer insulating film 161, 162: Contact 170: Barrier layer 173: Source region 175: Drain region 181, 111: Trench 190, 195: Interlayer insulating film 200: Transistor 500: Semiconductor devices

Claims

1. Strontium compounds represented by chemical formula 1: 【Chemistry 1】 In chemical formula 1, n is either 1 or 2. L2 is a second ligand that is different from the first ligand. A is a third ligand containing oxygen or nitrogen, m is between 0 and 4. L １ is the first ligand represented by chemical formula 2, 【Chemistry 2】 In chemical formula 2, X is nitrogen or CR (where R is hydrogen or a substituted or unsubstituted C1-C10 alkyl group), * indicates a part that is bonded to hydrogen or strontium (Sr). n １ is 1 or 2, n ２ These are, independently, 1 to 3, Y １ Each of these is either the same or different, independently, oxygen, or NR (where R is hydrogen or a substituted or unsubstituted C1-C10 alkyl group), R １ This is a substituted or unsubstituted C1-C5 alkyl group, or a Si-containing organic group. R ２ This is a substituted or unsubstituted C1-C5 alkyl group, or a Si-containing organic group.

2. The compound according to claim 1, having chemical formula 1, where n is 2.

3. The 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 acetylacetonate group, a substituted or unsubstituted diketonate residue, a substituted or unsubstituted ketoimminate residue, a substituted or unsubstituted β-ketostearate residue, a substituted or unsubstituted diimminate residue, a carbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted acetoxy group, a substituted or unsubstituted dialkylamide group, a substituted or unsubstituted acetamidinate group, a substituted or unsubstituted phenanthroline group, a substituted or unsubstituted glyoximate group, a substituted or unsubstituted carbamate group, a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted alkoxide group, a substituted or unsubstituted amidinate, a substituted or unsubstituted imidazolyl residue, a trispirazoleborate residue, or a combination thereof.

4. The first ligand is the compound according to claim 1, represented by chemical formula 2-1 or chemical formula 2-2: 【Transformation 3】 【Chemistry 4】 In chemical formula 2-1 or chemical formula 2-2, * indicates a part that is linked to hydrogen or strontium. n １ is 1 or 2, n ２ These are, independently, 1 to 3, R is hydrogen or a substituted or unsubstituted C1-C10 alkyl group. R １ is a substituted or unsubstituted C1-C5 alkyl group or a Si-containing organic group, R ２ This is a substituted or unsubstituted C1-C5 alkyl group, or a Si-containing organic group.

5. The first ligand is the compound according to claim 1, represented by chemical formula 2-3 or chemical formula 2-4: 【Transformation 5】 【Transformation 6】 In chemical formula 2-3 or chemical formula 2-4, * indicates a part that is linked to hydrogen or strontium. n １ is 1 or 2, n ２ These are, independently, 1 to 3, R is the same or different, independently of any other, hydrogen or a substituted or unsubstituted C1-C10 alkyl group. R １ This is a substituted or unsubstituted C1-C5 alkyl group, or a Si-containing organic group. R ２ This is a substituted or unsubstituted C1-C5 alkyl group, or a Si-containing organic group.

6. The compound according to claim 1, wherein the third ligand containing oxygen or nitrogen comprises a dialkoxyalkane, tetrahydrofuran, pyridine, dialkyl ether, or a combination thereof.

7. The compound according to claim 1, wherein the strontium compound does not contain the third ligand containing oxygen or nitrogen.

8. The strontium compound is the compound according to claim 1, which is represented by one of the following formulas: 【Transformation 7】

9. The strontium compound according to claim 1, wherein the strontium compound can be in a liquid state at temperatures of 20°C or higher and 50°C or lower.

10. A method for forming an oxide thin film, The method described above includes performing a strontium cycle to obtain a thin film containing a strontium-containing oxide, The aforementioned strontium cycle is A step in which strontium precursor gas is supplied to a process chamber containing the substrate; A step of supplying an inert gas to the process chamber to purge excess strontium precursor gas; and A step of providing the co-reactant, optionally together with an oxidizing agent, to the aforementioned process chamber; The process includes, by choice, a step of supplying an inert gas to the process chamber to purge excess co-reactant and, by choice, an oxidizing agent. The method comprising the strontium precursor gas described in claim 1.

11. The strontium compound is represented by chemical formula 2-1 or chemical formula 2-2, according to the method of claim 10: 【Transformation 8】 【Chemistry 9】 In chemical formula 2-1 or chemical formula 2-2, * indicates a part that is linked to hydrogen or strontium. n １ is 1 or 2, n ２ These are, independently, 1, 2, or 3. R is hydrogen or a substituted or unsubstituted C1-C10 alkyl group. R １ This is a substituted or unsubstituted C1-C5 alkyl group, or a Si-containing organic group. R ２ This is a substituted or unsubstituted C1-C5 alkyl group, or a Si-containing organic group.

12. The method according to claim 10, wherein the first ligand is represented by chemical formula 2-3 or chemical formula 2-4: 【Chemistry 10】 【Chemistry 11】 In chemical formula 2-3 or chemical formula 2-4, * indicates a part that is linked to hydrogen or strontium. n １ is 1 or 2, n ２ These are, independently, 1, 2, or 3. R is the same or different, independently of any other, hydrogen or a substituted or unsubstituted C1-C10 alkyl group. R １ This is a substituted or unsubstituted C1-C5 alkyl group, or a Si-containing organic group. R 2 This is a substituted or unsubstituted C1-C5 alkyl group, or a Si-containing organic group.

13. The strontium compound according to claim 10, which is represented by one of the following formulas: 【Chemistry 12】

14. The method further includes a first metal cycle, The first metallic cycle is, A step of supplying a first metal precursor gas to the process chamber; A step of supplying an inert gas to the process chamber to purge excess first metal precursor gas; and This includes supplying a reactant for the reaction with the first metal precursor to the process chamber, The method according to claim 10, wherein the first metal precursor includes titanium, barium, ruthenium, or a combination thereof.

15. The method according to claim 14, comprising multiple strontium cycles and multiple first metal cycles.

16. The method according to claim 10, wherein the co-reactant includes water vapor, oxygen, hydrogen, ozone, hydrogen peroxide, or a combination thereof.

17. A step of providing a transistor that is integrated on a semiconductor substrate or arranged on the semiconductor substrate, and The step of providing a capacitor that is electrically connected to the transistor. Includes, At least one of the steps of providing the transistor and providing the capacitor includes the step of forming an oxide thin film. The step of forming the oxide thin film is performed according to the method of claim 12 for manufacturing a semiconductor device.

18. The step of providing the capacitor is, Steps to form the first electrode, The step of forming the oxide thin film, and Steps to form the second electrode A method for manufacturing a semiconductor device according to claim 17, including the method described in claim 17.

19. The step of providing the aforementioned transistor is: The step of forming a trench in the semiconductor substrate, The steps of forming the oxide thin film in the trench, and The step of forming a gate conductor on the oxide thin film. A method for manufacturing a semiconductor device according to claim 17, including the method described in claim 17.

20. The aforementioned oxide thin film is strontium titanate (SrTiO ３ ), lanthanum strontium titanate, barium strontium titanate [Ba ｘ Sr １－ｘ TiO ３ A method for manufacturing a semiconductor device according to claim 17, comprising the formula (wherein 0 ≤ x ≤ 1), or a combination thereof.

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