Organometallic addition compound and method for manufacturing integrated circuit device using the same

Abstract

To provide an organometallic adduct compound, which may be used as a source compound capable of providing excellent thermal stability, process stability and mass productivity during the formation of a metal-containing film required for manufacture of an integrated circuit element, and a method of manufacturing an integrated circuit element using the compound.SOLUTION: The organometallic adduct compound is represented by the general formula I in the figure, where R1, R2 and R3 are each independently a C1-C5 alkyl group, provided that at least one of R1, R2 and R3 is a C1 to C5 alkyl group in which at least one H is substituted with a fluorine atom; M is a niobium atom, a tantalum atom, or a vanadium atom; X is a halogen atom; m is an integer of 3 to 5; and n is 1 or 2.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to an organometallic addition compound and a method for manufacturing an integrated circuit element using the same, and more particularly, to an organometallic addition compound containing niobium, tantalum, or vanadium as a metal and a method for manufacturing an integrated circuit element using the same.

Background Art

[0002] With the development of electronic technology, in recent years, the down-scaling of semiconductor elements has been rapidly advanced, and thereby, the patterns constituting the electronic elements have been miniaturized.

[0003] Along with this, when forming a metal-containing film necessary for manufacturing an integrated circuit element, it is an issue to develop a raw material compound for forming a metal-containing film that can provide excellent embedding characteristics and excellent step coverage characteristics, is easy to handle, and is advantageous in terms of process stability and mass productivity.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention has been made in view of the above problems in the manufacture of conventional integrated circuit elements, and an object of the present invention is to provide an organometallic addition compound that can be used as a raw material compound capable of providing excellent thermal stability, process stability, and mass productivity when forming a metal-containing film necessary for manufacturing an integrated circuit element. Another object of the present invention is to provide a method for manufacturing an integrated circuit device that can provide excellent process stability and mass productivity, and can provide desired electrical characteristics by forming a high-quality metal-containing film using a metal-containing raw material compound.

Means for Solving the Problems

[0006] The organometallic addition compound according to the present invention made to achieve the above object is characterized by being represented by the following general formula I.

Chemical formula

[0007] The method for manufacturing an integrated circuit device according to the present invention made to achieve the above object is characterized by having a step of forming a metal-containing film on a substrate using the organometallic addition compound of the general formula I.

Effects of the Invention

[0008] According to the organometallic addition compound of the present invention, it exhibits sufficient volatility for use in the vapor deposition process, has a relatively low melting point, a relatively high vapor pressure, is easy to handle and transport, and can form a high-quality metal-containing film with high productivity. In addition, the organometallic addition compound according to the present invention utilizes a CVD (chemical vapor deposition) process or an ALD (atomic layer deposition) process, suppressing the residual phenomenon of unwanted foreign substances such as carbon residues in the metal-containing film to be formed, being suitably used as a raw material for forming a metal-containing film with good quality, and being able to improve the productivity of the manufacturing process of integrated circuit elements.

Brief Description of Drawings

[0009]

Figure 1

Figure 2

Figure 3A

Figure 3B

Figure 3C

Figure 3D

Figure 4A

Figure 4B

Figure 4C

Figure 4D

Figure 4E

Figure 4F

Figure 4G

Figure 4H

Figure 4I

Figure 4J

Embodiments for Carrying Out the Invention

[0010] Next, specific examples of embodiments for carrying out the organometallic addition compound according to the present invention and the method for manufacturing an integrated circuit device using the same will be described with reference to the drawings.

[0011] For the same components in the drawings, the same reference numerals are used, and the overlapping descriptions related thereto are omitted. As used herein, the term "substrate" may mean a substrate itself or a laminated structure including the substrate and a predetermined layer or film formed on its surface. In addition, in this specification, the "surface of the substrate" may mean the exposed surface of the substrate itself or the outer surface of a predetermined layer or film formed on the substrate. As used herein, the term "room temperature" varies depending on the season and is about 20°C to about 28°C.

[0012] The organometallic addition compound according to an embodiment of the present invention has a structure in which an organophosphoric acid group is bonded to a coordination metal compound in the form of an adduct. The organometallic addition compound according to an embodiment of the present invention is represented by the following general formula I.

Chemical formula

[0013] In general formula I, R 1 , R 2 , and R 3 are each independently a C1-C5 alkyl group (for example, a substituted or unsubstituted C1-C5 alkyl group), and at least one of R 1 , R 2 , and R 3 is such that at least one hydrogen atom contained in the alkyl group is substituted with a fluorine atom. M is one element selected from the Group 5 elements of the periodic table, for example, a niobium atom, a tantalum atom, or a vanadium atom, X is a halogen atom, m is an integer from 3 to 5, and n is 1 or 2.

[0014] In an exemplary embodiment, at least one of R 1 , R 2 , and R 3 is a C1-C5 linear alkyl group. In another exemplary embodiment, at least one of R 1 , R 2 , and R 3 is a C3-C5 branched alkyl group.

[0015] In an exemplary embodiment, R 1 , R 2 , and R 3 are each independently a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a neopentyl group, or a 3-pentyl group. In another exemplary embodiment, R 1 , R 2 , and R 3 are each independently a trifluoromethyl group, a trifluoroethyl group, a hexafluoroisopropyl group, or a nonafluorotert-butyl group.

[0016] In general formula I, X can be an F atom, a Cl atom, a Br atom, or an I atom. When X is an F atom or a Cl atom, the melting point of the organometallic addition compound can be further lowered, and the vapor pressure of the organometallic addition compound can be further increased. The organometallic addition compound according to an embodiment of the present invention can be a liquid at normal temperature and normal pressure. If the organometallic addition compound is a liquid at normal temperature, it is easy to handle. In general formula I, when at least one of R 1 , R 2 , and R 3 is a branched alkyl group, it is also advantageous for the organometallic addition compound to be liquid at normal temperature.

[0017] In an exemplary embodiment, in general formula I, M is a niobium atom or a tantalum atom, and X can be a fluorine atom or a chlorine atom. In an exemplary embodiment, in general formula I, m is 5 and n can be 1. In an exemplary embodiment, in general formula I, M is a niobium atom or a tantalum atom, X is a chlorine atom, and R 1 , R 2 , and R 3 can each be a branched alkyl group.

[0018] In another exemplary embodiment, in General Formula I, M is a niobium atom or a tantalum atom, X is a fluorine atom, and R 1 , R 2 , and R 3 can each be a branched alkyl group. In yet another exemplary embodiment, in General Formula I, M is a niobium atom or a tantalum atom, X is a chlorine atom, and R 1 , R 2 , and R 3 can each be such that all hydrogen atoms contained in the alkyl group are substituted with fluorine atoms. In yet another exemplary embodiment, in General Formula I, M is a niobium atom or a tantalum atom, X is a fluorine atom, and R 1 , R 2 , and R 3 can each be such that all hydrogen atoms contained in the alkyl group are substituted with fluorine atoms.

[0019] The organometallic addition compound according to the present invention has a structure in which an organophosphoric acid group is bonded to a coordination metal compound in the form of an adduct. When used as a metal precursor in the formation of a metal-containing film by a CVD (chemical vapor deposition) process or an ALD (atomic layer deposition) process, during storage in a container, the organophosphoric acid group plays a role of protecting the coordination metal compound by a coordination bond. When transferred to a vapor deposition reaction chamber for forming a metal-containing film, it is easily decomposed by the process temperature in the reaction chamber and does not affect the surface reaction for forming the metal-containing film.

[0020] Specific examples of the organometallic addition compound according to the embodiment of the present invention are also represented by Chemical Formulas 1 to 16 shown below.

Chemical formula

Chemical formula

Chemical formula

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Chem.

[0021] The method for synthesizing the organometallic addition compound according to the embodiment of the present invention is not particularly limited, and can also be synthesized by applying well-known reactions. For example, in a dichloromethane solvent, from a solution obtained by reacting niobium pentachloride with a phosphate ester having a structure corresponding to the final structure to be synthesized at about 25°C, after distilling the solvent and unreacted substances, a method of distillation purification is utilized to synthesize an organometallic addition compound according to an embodiment of the present invention. The organometallic addition compound according to an embodiment of the present invention is also used as a raw material suitable for a CVD process or an ALD process.

[0022] FIG. 1 is a flowchart for explaining a method of manufacturing an integrated circuit element according to an embodiment of the present invention. Referring to FIG. 1, in step S10, a substrate is prepared. The substrate may also be made of silicon, ceramics, glass, metal, metal nitride, or a combination thereof. The ceramics may include silicon nitride, titanium nitride, tantalum nitride, titanium oxide, titanium nitride, niobium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, or a combination thereof.

[0023] The metal and the metal nitride may each include Ti, Ta, Co, Ru, Zr, Hf, La, or a combination thereof, but are not limited thereto. The surface of the substrate can have a flat plate shape, a spherical shape, a fiber shape, or a scale-like shape. Alternatively, the surface of the substrate can also have a three-dimensional structure such as a trench structure. In an exemplary embodiment, when referring to FIG. 4A, the substrate 310 can also have a configuration as described below.

[0024] In step S20 of FIG. 1, a metal-containing film forming raw material containing an organometallic addition compound of general formula I is used to form a metal-containing film on the substrate. The metal-containing film forming raw material contains an organometallic addition compound according to an embodiment of the present invention. In an exemplary embodiment, the raw material for forming the metal-containing film may include at least one organometallic addition compound among the organometallic addition compounds represented by Chemical Formula 1 to Chemical Formula 16. In an exemplary embodiment, the organometallic addition compound may be liquid at room temperature.

[0025] The raw material for forming the metal-containing film also varies depending on the thin film to be formed. In an exemplary embodiment, the metal-containing film to be formed may be composed of a niobium-containing film, a tantalum-containing film, or a vanadium-containing film. When forming a niobium-containing film, as the raw material for forming the metal-containing film, in the organometallic addition compound of General Formula I, one in which M is a niobium atom is used. When forming a tantalum-containing film, as the raw material for forming the metal-containing film, in the organometallic addition compound of General Formula I, one in which M is a tantalum atom is used. When forming a vanadium-containing film, as the raw material for forming the metal-containing film, in the organometallic addition compound of General Formula I, one in which M is a vanadium atom is used. In this case, the raw material for forming the metal-containing film contains only the organometallic addition compound according to the embodiment of the present invention and does not contain other metal compounds and metalloid compounds.

[0026] In other exemplary embodiments, the metal-containing film to be formed may further contain other metals in addition to niobium, tantalum, or vanadium. For example, when the metal-containing film to be formed further contains other metals or metalloids in addition to niobium, tantalum, or vanadium, the raw material for forming the metal-containing film may contain, in addition to the organometallic addition compound according to the embodiment of the present invention, a compound containing the desired metal or metalloid (hereinafter referred to as "other precursor"). In still other exemplary embodiments, the raw material for forming the metal-containing film may further contain an organic solvent or a nucleophilic reagent in addition to the organometallic addition compound according to the embodiment of the present invention.

[0027] To form the metal-containing film by step S20 of FIG. 1, a CVD process or an ALD process can be used. The raw material for forming a metal-containing film containing an organometallic addition compound according to an embodiment of the present invention can be suitably used in a chemical vapor deposition process such as a CVD process or an ALD process. When the raw material for forming a metal-containing film is used in a chemical vapor deposition process, the composition of the raw material for forming a metal-containing film can be appropriately selected according to its transport supply method.

[0028] As the raw material transport method, there are a gas transport method and a liquid transport method. In the gas transport method, inside the container in which the raw material for forming a metal-containing film is stored (hereinafter, also referred to as "raw material container"), the raw material is vaporized into a vapor state by heating or depressurization, and the vaporized raw material is, if necessary, used together with a carrier gas such as argon, nitrogen, or helium, and introduced into the inside of the chamber where the substrate is placed (hereinafter, also referred to as "deposition reaction section"). In the liquid transport method, the raw material is transported to the vaporization chamber in a liquid or solution state, vaporized into a vapor by heating and / or depressurization in the vaporization chamber, and then the vapor is introduced into the inside of the chamber.

[0029] When using the gas transport method to form the metal-containing film by step S20 of FIG. 1, the organometallic addition compound of general formula I itself can be used as the raw material for forming a metal-containing film. When using the liquid transport method to form the metal-containing film by step S20 of FIG. 1, the organometallic addition compound of general formula I itself or a solution in which the organometallic addition compound of general formula I is dissolved in an organic solvent can be used as the raw material for forming a metal-containing film. The raw material for forming a metal-containing film may further contain other precursors, nucleophilic reagents, etc.

[0030] In an exemplary embodiment, to form a metal-containing film by the method for manufacturing an integrated circuit element according to an embodiment of the present invention, a multi-component chemical vapor deposition method can be used. In the multi-component chemical vapor deposition method, a method of independently vaporizing and supplying the raw materials for forming a metal-containing film for each component (hereinafter, also described as "single source method"), or a multi-component raw material. A method of vaporizing and supplying a mixed raw material previously mixed in a desired composition (hereinafter, also described as "cocktail source method") can be used. When using the cocktail source method, a mixture of a precursor different from the organometallic addition compound according to the embodiment of the present invention, or a mixed solution obtained by dissolving the mixture in an organic solvent can be used as the raw material for forming the metal-containing film. The mixture or the mixed solution may further contain a nucleophilic reagent.

[0031] The type of the organic solvent is not particularly limited, and an organic solvent well-known in the art can be used. For example, as the organic solvent, acetic esters such as ethyl acetate, butyl acetate, and ethyl methoxyacetate, ethers such as tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and dibutyl ether, ketones such as dibutyl ketone, ethyl butyl ketone, diisobutyl ketone, methyl amyl ketone, and cyclohexanone, hydrocarbons such as hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, toluene, and xylene, hydrocarbons having a cyano group such as 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane, and 1,4-dicyanobenzene, pyridine, lutidine, etc. can be used. The above-exemplified organic solvents can be used alone or as a mixed solvent of at least two types in consideration of the solubility of the solute, the relationship between the use temperature, boiling point, and flash point.

[0032] When an organic solvent is included in a raw material for forming a metal-containing film containing an organometallic addition compound according to an embodiment of the present invention, the total amount of the organometallic addition compound and other precursors according to the embodiment of the present invention may be contained in the organic solvent in an amount of about 0.01 mol / L to about 2.0 mol / L, for example, about 0.05 mol / L to about 1.0 mol / L. Here, when the raw material for forming the metal-containing film does not contain other metal compounds and metalloid compounds other than the organometallic addition compound according to the embodiment of the present invention, the total amount is the amount of the organometallic addition compound according to the technical idea of the present invention. When the raw material for forming the metal-containing film further contains other metal compounds or metalloid compounds, that is, other precursors, in addition to the organometallic addition compound according to the embodiment of the present invention, the total amount is the sum of the amount of the organometallic addition compound according to the embodiment of the present invention and the amount of the other precursors.

[0033] When a multi-component chemical vapor deposition method is used to form a metal-containing film by a method for manufacturing an integrated circuit element according to an embodiment of the present invention, the types of other precursors that can be used together with the organometallic addition compound according to the embodiment of the present invention are not particularly limited, and well-known other precursors used as raw materials for forming the metal-containing film can be used. In an exemplary embodiment, examples of other precursors that can be used to form a metal-containing film by a method for manufacturing an integrated circuit element according to an embodiment of the present invention include at least one organic coordination compound selected from alcohol compounds, glycol compounds, β-diketone compounds, cyclopentadiene compounds, and organic amine compounds, and a compound containing any one selected from silicon and metal.

[0034] Other precursors may include elements such as lithium (Li), sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti), zirconium (Zr), hafnium (Hf), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), aluminum (Al), gallium (Ga), indium (In), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), but according to embodiments of the present invention, it is not limited to the aforementioned exemplified elements.

[0035] Examples of alcohol compounds that can be used as organic coordination compounds of other precursors include alkyl alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, pentyl alcohol, isopentyl alcohol, tert-pentyl alcohol, ether alcohols such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-methoxy-1-methylethanol, 2-methoxy-1,1-dimethylethanol, 2-ethoxy-1,1-dimethylethanol, 2-isopropoxy-1,1-dimethylethanol, 2-butoxy-1,1-dimethylethanol, 2-(2-methoxyethoxy)-1,1-dimethylethanol, 2-propoxy-1,1-diethylethanol, 2-sec-butoxy-1,1-diethylethanol, 3-methoxy-1,1-dimethylpropanol, and dialkylamino alcohols such as dimethylaminoethanol, ethylmethylaminoethanol, diethylaminoethanol, dimethylamino-2-pentanol, ethylmethylamino 2-pentanol, dimethylamino-2-methyl-2-pentanol, ethylmethylamino 2-methyl-2-pentanol, diethylamino-2-methyl-2-pentanol, but are not limited thereto.

[0036] Examples of glycol compounds that can be used as organic coordination compounds of other precursors include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 2,4-hexanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,3-butanediol, 2,4-butanediol, 2,2-diethyl-1,3-butanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,4-pentanediol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 2,4-hexanediol, and 2,4-dimethyl-2,4-pentanediol, but are not limited thereto.

[0037] Examples of β-diketone compounds that can be used as organic coordination compounds of other precursors include acetylacetone, hexane-2,4-dione, 5-methylhexane-2,4-dione, heptane-2,4-dione, 2-methylheptane-3,5-dione, 5-methylheptane-2,4-dione, 6-methylheptane-2,4-dione, 2,2-dimethylheptane-3,5-dione, dimethylheptane-3,5-dione, 2,2,6-trimethylheptane-3,5-dione, 2,2,6,6-tetramethylheptane-3,5-dione, octane-2,4-dione, 2,2,6-trimethyloctane-3,5-dione, 2,6-dimethyloctane-3,5-dione, 2,9-dimethylnonane-4,6-dione, 2-methyl-6-ethyldecane-3,5-dione, 2,2-dimethyl-6-ethyldecane-3,5-dione and other alkyl-substituted β-diketones, 1,1,1-trifluoropentane-2,4-dione, 1,1,1-trifluoro-5,5-dimethylhexane-2,4-dione, 1,1,1,5,5,5-hexafluoropentane-2,4-dione, 1,3-diperfluorohexylpropane-1,3-dione and other fluorine-substituted alkyl β-diketones, and 1,1,5,5-tetramethyl-1-methoxyhexane-2,4-dione, 2,2,6,6-tetramethyl-1-methoxyheptane-3,5-dione, 2,2,6,6-tetramethyl-1-(2-methoxyethoxy)heptane-3,5-dione and other ether-substituted β-diketones, but are not limited thereto.

[0038] Examples of cyclopentadiene compounds that can be used as organic coordination compounds of other precursors include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, sec-butylcyclopentadiene, isobutylcyclopentadiene, tert-butylcyclopentadiene, dimethylcyclopentadiene, tetramethylcyclopentadiene, etc., but are not limited thereto. Examples of organic amine compounds that can be used as organic coordination compounds of other precursors include, but are not limited to, methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, ethylmethylamine, propylmethylamine, isopropylmethylamine, and the like.

[0039] The above-mentioned other precursors are also known in the technical field to which the present invention pertains, and known methods can be utilized to manufacture them. For example, when an alcohol compound is used as the organic ligand, a precursor can be produced by reacting an inorganic salt of the aforementioned element or its hydrate with an alkali metal alkoxide of the alcohol compound. Here, examples of the inorganic salt of the aforementioned element or its hydrate include metal halides, nitrates, and the like. Examples of the alkali metal alkoxide include sodium alkoxide, lithium alkoxide, potassium alkoxide, and the like.

[0040] When the single-source method is utilized, as other precursors, compounds whose pyrolysis and / or oxidative decomposition behaviors are similar to those of the organometallic addition compounds according to the embodiments of the present invention can be used. When the cocktail-source method is utilized, as other precursors, those whose pyrolysis and / or oxidative decomposition behaviors are similar to those of the organometallic addition compounds according to the embodiments of the present invention and that do not cause deterioration due to chemical reactions or the like during mixing can be used.

[0041] In forming a metal-containing film by the method for manufacturing an integrated circuit element according to the embodiment of the present invention, the raw material for forming the metal-containing film may contain a nucleophilic reagent. According to the embodiment of the present invention, the nucleophilic reagent can impart stability to an organometallic addition compound containing a niobium atom, a tantalum atom, or a vanadium atom, and / or other precursors. The nucleophilic reagent can have ethylene glycol ethers such as glyme, diglyme, triglyme, and tetraglyme; crown ethers such as 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8, and dibenzo-24-crown-8; polyamines such as ethylenediamine, N,N'-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,1,4,7,7-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, and triethoxytriethylamine; cyclic polyamines such as cyclam and cyclen; heterocyclic compounds such as pyridine, pyrrolidine, piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, oxazole, thiazole, and oxathiolane; β-keto esters such as methyl acetoacetate, ethyl acetoacetate, and methoxyethyl 2-acetate; or β-diketones such as acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, and dipivaloylmethane. The amount of the nucleophilic reagent used is about 0.1 to about 10 moles, for example, about 1 to about 4 moles, per 1 mole of the total amount of the precursors.

[0042] In the metal-containing film-forming raw material used to form a metal-containing film by the method for manufacturing an integrated circuit element according to an embodiment of the present invention, it is necessary to minimize the amounts of impurity metal elements, impurity halogens such as impurity chlorine, and impurity organic substances. For example, in the metal-containing film-forming raw material, the impurity metal element is contained at about 100 ppb or less for each element. For example, the metal-containing film-forming raw material may contain an impurity metal element of about 10 ppb or less for each element, and the total amount of the impurity metal element is also about 1 ppm or less, for example, about 100 ppb or less.

[0043] In particular, when forming a thin film used as a gate insulating film, a gate conductive film, or a barrier film of an LSI (large scale integrated circuit), the contents of alkali metal elements and alkaline earth metal elements that affect the electrical characteristics of the obtained thin film should be minimized. For example, in a raw material for forming a metal-containing film, the impurity halogen component can be about 100 ppm or less, for example, about 10 ppm or less, or about 1 ppm or less. The impurity organic components that will be contained in the raw material for forming a metal-containing film are included even when the total amount of impurity organic components is about 500 ppm or less, for example, about 50 ppm or less, and in particular, even when about 10 ppm or less.

[0044] If moisture is contained in the raw material for forming a metal-containing film, it can cause particle generation in the raw material or particle generation during thin film formation. Therefore, the precursor, the organic solvent, and the nucleophilic reagent are pre-treated to remove moisture before use. The moisture content of each of the precursor, the organic solvent, and the nucleophilic reagent can be about 10 ppm or less, for example, about 1 ppm or less.

[0045] In the method for manufacturing an integrated circuit element, in forming a metal-containing film, in order to reduce particle contamination in the metal-containing film to be formed, the particle content can be minimized in the raw material for forming a metal-containing film. For example, when measuring particles by a light scattering type particle detector in a liquid state, in the raw material for forming a metal-containing film, the number of particles larger than 0.3 μm is 100 or less per 1 mL of the liquid, and the number of particles larger than 0.2 μm is 1,000 or less, for example, 100 or less per 1 mL of the liquid.

[0046] In step S20 of FIG. 1, in order to form a metal-containing film using a raw material for forming a metal-containing film, the raw material for forming a metal-containing film is vaporized, introduced into a deposition reaction section where the substrate is located, the raw material for forming a metal-containing film is deposited on the substrate surface, and a precursor thin film is formed on the substrate. The method includes reacting the precursor thin film with a reactive gas to form a metal-containing film containing niobium atoms, tantalum atoms, or vanadium atoms on the substrate surface. In order to vaporize the raw material for forming a metal-containing film and introduce it into the deposition reaction section, the aforementioned gas transport method, liquid transport method, single source method, cocktail source method, etc. can be used.

[0047] The reactive gas is a gas that reacts with the precursor thin film. For example, the reactive gas can consist of an oxidizing gas, a reducing gas, or a nitriding gas. The oxidizing gas can be selected from O2, O3, O2 plasma, H2O, NO2, NO, N2O, CO, CO2, H2O2, HCOOH, CH3COOH, (CH3CO)2O, alcohol, peroxide, sulfur oxide, or a combination thereof. The reducing gas is also H2. The nitriding gas can be selected from NH3, N2 plasma, organic amine compounds such as monoalkylamine, dialkylamine, trialkylamine, alkylene diamine, hydrazine compounds, or a combination thereof.

[0048] In step S20 of FIG. 1, when forming a metal oxide film containing niobium atoms, tantalum atoms, or vanadium atoms, an oxidizing gas is used as the reactive gas. In step S20 of FIG. 1, when forming a metal nitride film containing niobium atoms, tantalum atoms, or vanadium atoms, a nitriding gas is used as the reactive gas.

[0049] In an exemplary embodiment, in step S20 of FIG. 1, in order to form a metal-containing film containing niobium atoms, tantalum atoms, or vanadium atoms, a source gas containing an organometallic addition compound according to an embodiment of the present invention, or a source gas and a reactive gas, are reacted only by heat to form a thin film by a thermal CVD process, a plasma CVD process using heat and plasma, an optical CVD process using heat and light, an optical plasma CVD process using heat, light, and plasma, or an ALD process can be used.

[0050] In forming the metal-containing film by step S20 of FIG. 1, the reaction temperature (substrate temperature), reaction pressure, deposition rate, etc. are appropriately selected according to the desired thickness and type of the metal-containing film. The reaction temperature can also be selected from the range of room temperature to about 500°C, for example, about 150°C to about 400°C, which is a temperature at which the source for forming the metal-containing film can sufficiently react.

[0051] In forming the metal-containing film by step SP20 of FIG. 1, when using the ALD process, the number of cycles of the ALD process is adjusted to adjust the film thickness of the metal-containing film. When using the ALD process to form a metal-containing film on a substrate, a source gas introduction step of introducing a vapor formed by vaporizing a source for forming a metal-containing film containing an organometallic addition compound according to an embodiment of the present invention into a deposition reaction section, a precursor thin film forming step of forming a precursor thin film on the surface of the substrate using the vapor, an exhaust step of exhausting unreacted source gas remaining in the reaction space on the substrate, and a step of chemically reacting the precursor thin film with a reactive gas to form a metal-containing film on the surface of the substrate may be included.

[0052] In an exemplary embodiment, the step of vaporizing the source for forming the metal-containing film is performed in a source container and is also performed in a vaporization chamber. The step of vaporizing the source for forming the metal-containing film is also performed at about 0°C to about 200°C. When vaporizing the source for forming the metal-containing film, the pressure inside the source container or the vaporization chamber can be about 1 Pa to about 10,000 Pa.

[0053] Figure 2 is a flowchart for specifically explaining an exemplary method for forming a metal-containing film by a method for manufacturing an integrated circuit element according to an embodiment of the present invention. Referring to Figure 2, a method for forming a metal-containing film in the ALD process in step S20 of Figure 1 will be described.

[0054] Referring to Figure 2, in step S21, a source gas containing an organometallic addition compound having the structure of General Formula I is vaporized. In an exemplary embodiment, the source gas may consist of the aforementioned raw material for forming the metal-containing film. The step of vaporizing the source gas is performed at about 0°C to about 200°C. When vaporizing the source gas, the pressure inside the raw material container or the vaporization chamber is about 1 Pa to about 10,000 Pa.

[0055] In step S22, the source gas vaporized in step P21 is supplied onto the substrate, and a metal source adsorption layer containing niobium atoms, tantalum atoms, or vanadium atoms is formed on the substrate. At this time, the reaction temperature is selected within the range of room temperature to about 500°C, for example, about 150°C to about 400°C. The reaction pressure is about 1 Pa to about 10,000 Pa, for example, about 10 Pa to about 1,000 Pa. By supplying the vaporized source gas onto the substrate, an adsorption layer including a chemisorbed layer and a physisorbed layer of the vaporized source gas is formed on the substrate.

[0056] In step S23, a purge gas is supplied onto the substrate to remove unnecessary by-products on the substrate. As the purge gas, for example, an inert gas such as Ar, He, Ne, or N2 gas can be used. In another exemplary embodiment, instead of the purge step, the reaction space where the substrate is located can be depressurized and evacuated. At this time, for pressure reduction, the pressure in the reaction space is maintained at about 0.01 Pa to about 300 Pa, for example, about 0.01 Pa to about 100 Pa.

[0057] In an exemplary embodiment, a step of heating a substrate on which a metal source adsorption layer containing niobium atoms, tantalum atoms, or vanadium atoms is formed, or heat-treating a reaction chamber containing the substrate can be further performed. The heat treatment is performed at a temperature from room temperature to about 500 °C, for example, about 50 °C to about 400 °C.

[0058] In step S24, a reactive gas is supplied onto the metal source adsorption layer formed on the substrate to form a metal-containing film in atomic layer units. In an exemplary embodiment, when forming a metal oxide film containing niobium atoms, tantalum atoms, or vanadium atoms on the substrate, the reactive gas can be an oxidizing gas selected from O2, O3, O2 plasma, H2O, NO2, NO, N2O (nitrous oxide), CO, CO2, H2O2, HCOOH, CH3COOH, (CH3CO)2O, alcohol, peroxide, sulfur oxide, or a combination thereof. In another exemplary embodiment, when forming a metal nitride film containing niobium atoms, tantalum atoms, or vanadium atoms on the substrate, the reactive gas is selected from NH3, N2 plasma, monoalkylamine, dialkylamine, trialkylamine, organic amine compound, hydrazine compound, or a combination thereof. In still another exemplary embodiment, the reactive gas can be a reducing gas, for example, H2.

[0059] During the execution of step S24, the reaction space is maintained at a temperature from room temperature to about 500 °C, for example, about 50 °C to about 400 °C, or about 50 °C to about 200 °C, so that the metal source adsorption layer containing niobium atoms, tantalum atoms, or vanadium atoms and the reactive gas react sufficiently. During the execution of step S24, the pressure in the reaction space can be about 1 Pa to about 10,000 Pa, for example, about 10 Pa to about 1,000 Pa. While executing step S24, the reactive gas is subjected to plasma treatment. The high-frequency (RF) output during plasma treatment can be from about 0 W to about 1,500 W, for example, from about 50 W to about 600 W.

[0060] In step S25, a purge gas is supplied onto the substrate to remove unnecessary by-products on the substrate. As the purge gas, for example, an inert gas such as Ar, He, Ne, or N2 gas can be used.

[0061] In step S26, steps S21 to S25 in FIG. 2 are repeated until a metal-containing film with a desired thickness is formed. A thin film deposition process consisting of a series of steps from step S21 to step S25 is defined as one cycle, and the above cycle is repeated multiple times until a metal-containing film with a desired thickness is formed. In an exemplary embodiment, after performing the aforementioned one cycle, similar to step S23 or step S25, an evacuation process using a purge gas is performed to evacuate unreacted gas from the reaction chamber, and then subsequent cycles can be executed.

[0062] In an exemplary embodiment, in order to control the deposition rate of the metal-containing film, raw material supply conditions (for example, the vaporization temperature or vaporization pressure of the raw material), reaction temperature, reaction pressure, etc. can be controlled. If the deposition rate of the metal-containing film becomes excessively fast, the characteristics of the obtained metal-containing film will deteriorate, and if the deposition rate of the metal-containing film is excessively slow, the productivity will decrease. For example, the deposition rate of the metal-containing film can be from about 0.01 nm / min to about 100 nm / min, for example, from about 1 nm / min to about 50 nm / min.

[0063] The process for forming the metal-containing film described with reference to FIG. 2 is merely an example, and within the scope of the technical idea of the present invention, various modifications and changes are possible. For example, in order to form a metal-containing film on a substrate, an organometallic addition compound having the structure of General Formula I can be supplied onto the substrate together with or sequentially with at least one of other precursors, reactive gases, carrier gases, and purge gases. The more detailed configurations of other precursors, reactive gases, carrier gases, and purge gases that can be supplied onto the substrate together with the organometallic addition compound having the structure of General Formula I are as described above. In another exemplary embodiment, in the step of forming the metal-containing film described with reference to FIG. 2, a reactive gas can be supplied onto the substrate between each of steps S21 to S25.

[0064] FIGS. 3A to 3D are diagrams schematically showing the configurations of exemplary vapor deposition apparatuses (200A, 200B, 200C, 200D) that can be used in the step of forming a metal-containing film in a method for manufacturing an integrated circuit element according to an embodiment of the present invention. The vapor deposition apparatuses (200A, 200B, 200C, 200D) illustrated in FIGS. 3A to 3D each include a fluid transfer unit 210, a thin film forming unit 250 in which a deposition process for forming a thin film on a substrate W is performed using a process gas supplied from a raw material container 212 in the fluid transfer unit 210, and an exhaust system 270 for discharging the gas remaining after being used in the reaction or reaction by-products in the thin film forming unit 250.

[0065] The thin film forming unit 250 includes a reaction chamber 254 equipped with a susceptor 252 for supporting the substrate W. At the upper end inside the reaction chamber 254, a shower head 256 for supplying the gas supplied from the fluid transfer unit 210 onto the substrate W is provided. The fluid transfer unit 210 includes an inflow line 222 for supplying a carrier gas from the outside to the raw material container 212 and an outflow line 224 for supplying the raw material compound accommodated in the raw material container 212 to the thin film forming unit 250. Valves (V1, V2) and MFCs (mass flow controllers) (M1, M2) are provided in the inflow line 222 and the outflow line 224, respectively. The inflow line 222 and the outflow line 224 are interconnected via a bypass line 226. A valve V3 is provided in the bypass line 226. The valve V3 can be pneumatically actuated by an electric motor or other remotely controllable means.

[0066] The raw material compound supplied from the raw material container 212 is also supplied into the reaction chamber 254 through an inflow line 266 of a thin film forming unit 250 connected to the outflow line 224 of the fluid transfer unit 210. If necessary, the raw material compound supplied from the raw material container 212 is also supplied into the reaction chamber 254 together with a carrier gas supplied through an inflow line 268. A valve V4 and an MFC (M3) are provided in the inflow line 268 through which the carrier gas flows in. The thin film forming unit 250 includes an inflow line 262 for supplying a purge gas into the reaction chamber 254 and an inflow line 264 for supplying a reactive gas. Valves (V5, V6) and MFCs (M4, M5) are provided in the inflow lines (262, 264), respectively.

[0067] The process gas used in the reaction chamber 254 and the reaction by-products for disposal are discharged to the outside through an exhaust system 270. The exhaust system 270 may include an exhaust line 272 connected to the reaction chamber 254 and a vacuum pump 274 provided in the exhaust line 272. The vacuum pump 274 serves to remove the process gas discharged from the reaction chamber 254 and the reaction by-products for disposal. In the exhaust line 272, a trap 276 is provided upstream of the vacuum pump 274.

[0068] The trap 276 captures, for example, reaction by-products generated by process gases that could not fully react in the reaction chamber 254 and blocks the inflow to the downstream vacuum pump 274. In the trap 276 provided in the exhaust line 272, it serves to capture deposits such as reaction by-products generated by the reaction between process gases and prevent them from flowing to the downstream side of the trap 276. The trap 276 can have a configuration that can be cooled by a freezer or water cooling. Also, in the exhaust line 272, a bypass line 278 and an automatic pressure controller 280 are provided upstream of the trap 276. Valves (V7, V8) are provided in the bypass line 278 and in the portion of the exhaust line 272 that extends in parallel with the bypass line 278, respectively.

[0069] In the vapor deposition apparatuses (200A, 200C) illustrated in FIGS. 3A and 3C, a heater 214 is provided in the raw material container 212. The heater 214 maintains the temperature of the raw material compound accommodated in the raw material container 212 at a relatively high temperature. In the vapor deposition apparatuses (200B, 200D) illustrated in FIGS. 3B and 3D, a vaporizer 258 is provided in the inflow line 266 of the thin film forming section 250. The vaporizer 258 vaporizes the fluid supplied in liquid form from the fluid transfer section 210 and supplies the vaporized raw material compound into the reaction chamber 254. The raw material compound vaporized by the vaporizer 258 is supplied into the reaction chamber 254 together with the carrier gas supplied through the inflow line 268. The inflow of the raw material compound supplied to the reaction chamber 254 through the vaporizer 258 is controlled by the valve V9. Also, in the vapor deposition apparatuses (200C, 200D) illustrated in FIGS. 3C and 3D, in the thin film forming section 250, a high-frequency power supply 292 and an RF matching system 294 connected to the reaction chamber 254 are included to generate plasma in the reaction chamber 254.

[0070] In the vapor deposition apparatuses (200A, 200B, 200C, 200D) illustrated in FIGS. 3A to 3D, a configuration in which one raw material container 212 is connected to the reaction chamber 254 is illustrated, but the present invention is not limited thereto. If necessary, the fluid transfer unit 210 can be provided with a plurality of raw material containers 212, and the plurality of raw material containers 212 are each connected to the reaction chamber 254. The number of raw material containers 212 connected to the reaction chamber 254 is not particularly limited. In order to vaporize the raw material for forming a metal-containing film containing the organometallic addition compound of General Formula I, the vaporizer 258 can be used in any one of the vapor deposition apparatuses (200B, 200D) illustrated in FIGS. 3B and 3D, but the technical idea of the present invention is not limited thereto.

[0071] By the method for manufacturing an integrated circuit element described with reference to FIGS. 1 and 2, any one of the vapor deposition apparatuses (200A, 200B, 200C, 200D) illustrated in FIGS. 3A to 3D can be used to form a metal-containing film on a substrate. Therefore, the organometallic addition compound according to the embodiment of the present invention having the structure of General Formula I is transported through various methods and is also supplied into the reaction space of the thin film forming apparatus, for example, inside the reaction chamber 254 of the vapor deposition apparatuses (200A, 200B, 200C, 200D) illustrated in FIGS. 3A to 3D. In an exemplary embodiment, by the method described with reference to FIGS. 1 and 2, instead of a single wafer type facility such as the vapor deposition apparatuses (200A, 200B, 200C, 200D) illustrated in FIGS. 3A to 3D, a batch type facility can be used to form a metal-containing film on a number of substrates simultaneously.

[0072] When forming a metal-containing film by the method for manufacturing an integrated circuit element according to an embodiment of the present invention, examples of the formation conditions of the metal-containing film include reaction temperature (substrate temperature), reaction pressure, deposition rate, and the like. The reaction temperature is a temperature at which the organometallic addition compound according to the embodiment of the present invention, for example, the organometallic addition compound having the structure of General Formula I can sufficiently react, that is, as an example, a temperature of about 150 °C or higher, as another example, a temperature in the range of about 150 °C to about 400 °C, and as still another example, a temperature range selected from about 200 °C to about 350 °C, but is not limited to the exemplified temperatures.

[0073] The reaction pressure is selected from the range of about 10 Pa to atmospheric pressure in the case of a thermal CVD process or a photo CVD process, and from the range of about 10 Pa to 2,000 Pa in the case of using plasma, but is not limited thereto. In addition, the deposition rate can be controlled by adjusting the supply conditions of the raw material compound (for example, vaporization temperature and vaporization pressure), reaction temperature, and reaction pressure. In the method for forming a metal-containing film according to the embodiment of the present invention, the deposition rate of the metal-containing film can be selected from the range of about 0.01 nm / min to about 100 nm / min, for example, from the range of about 1 nm / min to about 50 nm / min, but is not limited to the exemplified values.

[0074] When forming a metal-containing film using an ALD process, the number of ALD cycles is adjusted to control the metal-containing film having a desired thickness. According to the embodiment of the present invention, when forming a metal-containing film using an ALD process, energy such as plasma, light, and voltage can be applied. The timing of applying energy can be variously selected. For example, when introducing a source gas containing an organometallic addition compound into the reaction chamber, when adsorbing the source gas onto the substrate, during the evacuation process with a purge gas, when introducing a reactive gas into the reaction chamber, or between each of these times, energy such as plasma, light, and voltage can be applied.

[0075] According to the embodiment of the present invention, after forming a metal-containing film using an organometallic addition compound having the structure of General Formula I, an annealing step may further be included under an inert atmosphere, an oxidizing atmosphere, or a reducing atmosphere. Alternatively, in order to fill the steps formed on the surface of the metal-containing film, a reflow process can be performed on the metal-containing film if necessary. The annealing process and the reflow process are each performed under temperature conditions selected from the range of about 200°C to about 1,000°C, for example, about 250°C to about 500°C, but are not limited to the exemplified temperatures.

[0076] According to an embodiment of the present invention, by appropriately selecting the organometallic addition compound according to the embodiment of the present invention, other precursors used together with the organometallic addition compound, the reactive gas, and the thin film forming process conditions, various types of metal-containing films can be formed. In an exemplary embodiment, the metal-containing film formed according to an embodiment of the present invention may contain niobium atoms, tantalum atoms, or vanadium atoms. For example, the metal-containing film may include a niobium film, a niobium oxide film, a niobium nitride film, a niobium alloy film, a niobium-containing composite oxide film, a tantalum film, a tantalum oxide film, a tantalum nitride film, a tantalum alloy film, a tantalum-containing composite oxide film, and the like. The niobium alloy film may also be composed of Nb·Hf alloy, Nb·Ti alloy, etc., but is not limited to those exemplified. The tantalum alloy film may also be composed of Ta·Ti alloy, Ta·W alloy, etc., but is not limited to those exemplified.

[0077] The metal-containing film formed according to an embodiment of the present invention is also used as a material for various components constituting an integrated circuit element. For example, it is also used for the electrode material of a DRAM (dynamic random access memory) element, the gate of a transistor, a resistor, an antiferromagnetic film used for a hard device recording layer, a catalyst material for a solid polymer fuel cell, a conductive barrier film used for metal wiring, a dielectric film of a capacitor, a barrier metal film for liquid crystal, a member for a thin film solar cell, a member for semiconductor equipment, a nanostructure, etc., but the use of the metal-containing film is not limited to the exemplified elements described above.

[0078] Figures 4A to 4J are cross-sectional views shown in the order of processes for explaining a method of manufacturing an integrated circuit element 300 (Figure 4J) according to an embodiment of the present invention. Referring to Figure 4A, after forming an interlayer insulating film 320 on a substrate 310 including a plurality of active regions AC, a plurality of conductive regions 324 penetrating the interlayer insulating film 320 and connected to the plurality of active regions AC are formed.

[0079] The substrate 310 may include a semiconductor such as Si or Ge, or a compound semiconductor such as SiGe, SiC, GaAs, InAs, or InP. The substrate 310 may include a conductive region, for example, a well doped with an impurity or a structure doped with an impurity. The plurality of active regions AC are defined by a plurality of element isolation regions 312 formed in the substrate 310. The element isolation region 312 is made of a silicon oxide film, a silicon nitride film, a silicon oxynitride film, or a combination thereof. The interlayer insulating film 320 may include a silicon oxide film. The plurality of conductive regions 324 are connected to one terminal of a switching element (not shown) such as a field effect transistor formed on the substrate 310. The plurality of conductive regions 324 are made of polysilicon, metal, conductive metal nitride, metal silicide, or a combination thereof.

[0080] Referring to Figure 4B, an insulating layer 328 covering the interlayer insulating film 320 and the plurality of conductive regions 324 is formed. The insulating layer 328 is used as an etching stop layer. The insulating layer 328 is made of an insulating material having an etching selectivity with respect to the interlayer insulating film 320 and a mold film 330 (Figure 4C) formed in a subsequent process. The insulating layer 328 is made of silicon nitride, silicon oxynitride, or a combination thereof.

[0081] Referring to Figure 4C, a mold film 330 is formed on the insulating layer 328. The mold film 330 is made of an oxide film. For example, the mold film 330 may include an oxide film such as BPSG (borophospho silicate glass), PSG (phospho silicate glass), or USG (undoped silicate glass). To form the mold film 330, a thermal CVD process or a plasma CVD process can be utilized. The mold film 330 is formed to have a thickness of about 1,000 Å to about 20,000 Å, but is not limited thereto.

[0082] In an exemplary embodiment, the mold film 330 may include a support film (not shown). The support film is formed of a material having an etching selectivity ratio with respect to the mold film 330. The support film is made of a material having a relatively low etching rate with respect to an etching atmosphere used to remove the mold film 330 in a subsequent process, for example, an etching solution containing ammonium fluoride (NH4F), hydrofluoric acid (HF), and water. In an exemplary embodiment, the support film is made of silicon nitride, silicon carbonitride, tantalum oxide, titanium oxide, or a combination thereof.

[0083] Referring to FIG. 4D, a sacrificial film 342 and a mask pattern 344 are sequentially formed on the mold film 330. The sacrificial film 342 is made of an oxide film. The mask pattern 344 is made of an oxide film, a nitride film, a polysilicon film, a photoresist film, or a combination thereof. The mask pattern 344 defines a region where the lower electrode of the capacitor is formed.

[0084] Referring to FIG. 4E, the mask pattern 344 is used as an etching mask, the insulating layer 328 is used as an etching stop layer, and the sacrificial film 342 and the mold film 330 are dry-etched to form a sacrificial pattern 342P and a mold pattern 330P that define a plurality of holes H1. At this time, due to over-etching, the insulating layer 328 is also etched, and an insulating pattern 328P that exposes a plurality of conductive regions 324 is formed.

[0085] Referring to FIG. 4F, after removing the mask pattern 344 from the result of FIG. 4E, a conductive film 350 for forming a lower electrode is formed while filling the plurality of holes H1 and covering the exposed surface of the sacrificial pattern 342P. The conductive film 350 for forming a lower electrode is made of a doped semiconductor, a conductive metal nitride, a metal, a metal silicide, a conductive oxide, or a combination thereof. In an exemplary embodiment, the conductive film 350 for forming a lower electrode is made of a doped semiconductor, a conductive metal nitride, a metal, a metal silicide, a conductive oxide, or a combination thereof.

[0086] For example, the conductive film 350 for forming a lower electrode is made of NbN, TiN, TiAlN, TaN, TaAlN, W, WN, Ru, RuO2, SrRuO3, Ir, IrO2, Pt, PtO, SRO (SrRuO3), BSRO ((Ba,Sr)RuO3), CRO (CaRuO3), LSCo ((La,Sr)CoO3), or a combination thereof. However, the constituent material of the conductive film 350 for forming a lower electrode is not limited to those exemplified. To form the conductive film 350 for forming a lower electrode, a CVD process, a MOCVD (metalorganic CVD) process, or an ALD process can be used.

[0087] In an exemplary embodiment, to form the conductive film 350 for forming a lower electrode, a metal-containing film can be formed by the method described with reference to step S20 of FIG. 1 or FIG. 2. For example, the conductive film 350 for forming the lower electrode can have a multilayer structure including a TiN film and a NbN film. The NbN film is a film formed by the method described with reference to step S20 in FIG. 1 or the method described with reference to FIG. 2. To form the conductive film 350 for forming the lower electrode, any one of the vapor deposition apparatuses (200A, 200B, 200C, 200D) illustrated in FIGS. 3A to 3D can be used.

[0088] Referring to FIG. 4G, the upper part of the conductive film 350 for forming the lower electrode is partially removed, and a plurality of lower electrodes LE are formed from the conductive film 350 for forming the lower electrode. To form a plurality of lower electrodes LE, an etchback or CMP (chemical mechanical polishing) process is used until the upper surface of the mold pattern 330P is exposed, and a part of the upper side of the conductive film 350 for forming the lower electrode and the sacrificial pattern 342P (FIG. 4F) are removed.

[0089] Referring to FIG. 4H, the mold pattern 330P is removed from the result of FIG. 4G, and the outer surfaces of the plurality of lower electrodes LE are exposed. The mold pattern 330P is removed by a lift-off process using an etching solution containing ammonium fluoride (NH4F), hydrofluoric acid (HF), and water.

[0090] Referring to FIG. 4I, a dielectric film 360 is formed on the plurality of lower electrodes LE. The dielectric film 360 is formed so as to conformally cover the exposed surfaces of the plurality of lower electrodes LE. In an exemplary embodiment, the dielectric film 360 is made of hafnium oxide, hafnium oxynitride, hafnium silicon oxide, zirconium oxide, zirconium silicon oxide, tantalum oxide, titanium oxide, barium strontium titanate, barium titanate, strontium titanate, yttrium oxide, aluminum oxide, lead scandium tantalate, lead zinc niobate, or a combination thereof, but is not limited to those exemplified.

[0091] The dielectric film 360 is formed by an ALD process. In an exemplary embodiment, in order to form at least a part of the dielectric film 360, a metal-containing film can be formed by the method described with reference to step S20 of FIG. 1 or the method described with reference to FIG. 2. For example, the dielectric film 360 may include a tantalum oxide film, and the tantalum oxide film is a film formed by the method described with reference to step S20 of FIG. 1 or the method described with reference to FIG. 2. To form the dielectric film 360, any one of the vapor deposition apparatuses (200A, 200B, 200C, 200D) exemplified in FIGS. 3A to 3D can be used. The dielectric film 360 can have a thickness of about 50 to 150 Å, but is not limited thereto.

[0092] In an exemplary embodiment, as described with reference to FIG. 4I, before forming the dielectric film 360 on the plurality of lower electrodes LE, a step of forming a lower interface film (not shown) covering the surfaces of the plurality of lower electrodes LE may be further included. In that case, the dielectric film 360 is also formed on the lower interface film. The lower interface film is made of a metal-containing film containing niobium, tantalum, or vanadium. To form the metal-containing film constituting the lower interface film, the method described with reference to step S20 of FIG. 1 or the method described with reference to FIG. 2 can be used. To form the lower interface film, any one of the vapor deposition apparatuses (200A, 200B, 200C, 200D) illustrated in FIGS. 3A to 3D can be used.

[0093] Referring to FIG. 4J, an upper electrode UE is formed on the dielectric film 360. The lower electrode LE, the dielectric film 360, and the upper electrode UE constitute a capacitor 370. The upper electrode UE is made of a doped semiconductor, a conductive metal nitride, a metal, a metal silicide, a conductive oxide, or a combination thereof. For example, the upper electrode UE is made of NbN, TiN, TiAlN, TaN, TaAlN, W, WN, Ru, RuO2, SrRuO3, Ir, IrO2, Pt, PtO, SRO (SrRuO3), BSRO ((Ba, Sr) RuO3), CRO (CaRuO3), LSCo ((La, Sr) CoO3), or a combination thereof, but is not limited thereto.

[0094] To form the upper electrode UE, a CVD process, a MOCVD process, a PVD process, or an ALD process can be used. In an exemplary embodiment, to form the upper electrode UE, the metal-containing film can be formed by the method described with reference to step S20 of FIG. 1 or FIG. 2. To form the upper electrode UE, any one of the vapor deposition apparatuses (200A, 200B, 200C, 200D) illustrated in FIGS. 3A to 3D can be used.

[0095] In an exemplary embodiment, as described with reference to FIG. 4J, before forming the upper electrode UE on the dielectric film 360, a step of forming an upper interface film (not shown) covering the surface of the dielectric film 360 may be further included. In that case, the upper electrode UE is also formed on the upper interface film. The upper interface film is made of a metal-containing film containing niobium, tantalum, or vanadium. To form the metal-containing film constituting the upper interface film, the method described with reference to step S20 of FIG. 1 or FIG. 2 can be used. To form the upper interface film, any one of the vapor deposition apparatuses (200A, 200B, 200C, 200D) illustrated in FIGS. 3A to 3D can be used.

[0096] In the method for manufacturing an integrated circuit element described with reference to FIGS. 4A to 4J, the case where a plurality of lower electrodes LE have a pillar shape is described as an example, but the present invention is not limited thereto. For example, each of the plurality of lower electrodes LE can have a cup shape or a cylindrical cross-sectional structure with a blocked bottom.

[0097] In the integrated circuit element 300 manufactured by the method as described with reference to FIGS. 4A to 4J, the capacitor 370 includes a lower electrode LE having a three-dimensional electrode structure. To compensate for the capacitance reduction due to design rule reduction, the aspect ratio of the lower electrode LE having a three-dimensional structure is increasing, and an ALD process can be used to form a high-quality dielectric film 360 in a deep and narrow three-dimensional space.

[0098] According to the method for manufacturing an integrated circuit element according to the embodiment of the present invention described with reference to FIGS. 4A to 4J, in forming the lower electrode LE, the dielectric film 360, or the upper electrode UE, the process stability can be improved by using the organometallic addition compound according to the embodiment of the present invention of General Formula I.

[0099] Next, a specific synthesis example of the organometallic addition compound according to the embodiment of the present invention and a method for forming a metal-containing film will be described. However, the organometallic addition compound and the method for forming a metal-containing film according to the embodiment of the present invention are not limited to the following examples.

[0100] <<Synthesis Example>> <Synthesis Example 1> [Synthesis of the compound of Chemical Formula 2] Under an Ar atmosphere, 9.40 g (50.0 mmol) of niobium pentafluoride and 250 ml of dehydrated dichloromethane were added to a 500 mL four-necked flask, and the mixture was stirred while maintaining the temperature of the resulting liquid at 25 °C. Then, at room temperature, 17.7 g (51.5 mmol) of tris(2,2,2-trifluoroethyl) phosphate was added dropwise and the mixture was stirred for 5 hours. Under reduced pressure, the solvent and unreacted tris(2,2,2-trifluoroethyl) phosphate were distilled off, and then purified by distillation to obtain 10.2 g (yield 38.2%) of the target product. (Analytical values) (1) 1 H-NMR (benzene-d6) 3.70 ppm (6H, multiplet) (2)Elemental analysis (theoretical values) Nb: 17.9% (17.5%), C: 14.0% (13.6%), H: 1.6% (1.1%), F: 50.7% (50.0%), P: 6.1% (5.8%)

[0101] [Synthesis Example 2] [Synthesis of the compound of Chemical Formula 6] Under an Ar atmosphere, 13.5 g (50.0 mmol) of niobium pentachloride and 300 ml of dehydrated dichloromethane were added to a 500 mL four-necked flask, and the mixture was stirred while maintaining the temperature of the resulting liquid at 25 °C. Then, at room temperature, 17.7 g (51.5 mmol) of tris(2,2,2-trifluoroethyl) phosphate was added dropwise and the mixture was stirred for 5 hours. Under reduced pressure, the solvent and unreacted tris(2,2,2-trifluoroethyl) phosphate were distilled off, and then purified by distillation to obtain 28.0 g (yield 91.2%) of the target product. (Analytical values) (1) 1 H-NMR (benzene-d6) 3.87 ppm (6H, doublet of quarted) (2)Elemental analysis (theoretical values) Nb: 15.5% (15.1%), C: 12.0% (11.7%), H: 1.4% (1.0%), Cl: 29.3% (28.9%), F: 28.2% (27.8%), P: 5.1% (5.0%)

[0102] <Synthesis Example 3> [Synthesis of the compound of Chemical Formula 7] Under an Ar atmosphere, 13.5 g (50.0 mmol) of niobium pentachloride and 300 ml of dehydrated dichloromethane were added to a 500 mL four-necked flask, and the mixture was stirred while maintaining the liquid temperature at 25 °C. Then, at room temperature, 28.2 g (51.5 mmol) of tris(1,1,1,3,3,3-hexafluoro-2-propyl) phosphate was added dropwise and stirred for 5 hours. Under reduced pressure, the solvent and unreacted tris(1,1,1,3,3,3-hexafluoro-2-propyl) phosphate were distilled off, and then purified by distillation to obtain 20.5 g (yield 50.2%) of the target product. (Analysis values) (1) 1 H-NMR (benzene-d6) 4.81 ppm (3H, singlet, broad) (2) Elemental analysis (theoretical values) Nb: 11.5% (11.4%), C: 13.5% (13.2%), H: 0.8% (0.4%), Cl: 22.0% (21.7%), F: 42.0% (41.8%), P: 4.1% (3.8%)

[0103] <Synthesis Example 4> [Synthesis of the compound of Chemical Formula 14] Under an Ar atmosphere, 17.9 g (50.0 mmol) of TaCl5 and 300 ml of dehydrated dichloromethane were added to a 500 mL four-necked flask, and the mixture was stirred while maintaining the liquid temperature at 25 °C. Then, at room temperature, 17.7 g (51.5 mmol) of tris(2,2,2-trifluoroethyl) phosphate was added dropwise and stirred for 5 hours. Under reduced pressure, the solvent and unreacted tris(2,2,2-trifluoroethyl) phosphate were distilled off, and then purified by distillation to obtain 30.9 g (yield 87.9%) of the target product. (Analysis values) (1) 1 1H-NMR (in deuterated benzene) 3.85 ppm (6H, doublet of quartets) (2) Elemental analysis (theoretical values) Ta: 25.9% (25.8%), C: 10.7% (10.3%), H: 1.1% (0.9%), Cl: 25.7% (25.2%), F: 24.6% (24.4%), P: 4.4% (4.4%)

[0104] <<Evaluation Examples 1 to 4 and Comparative Evaluation Examples 1 to 4>> Next, for the compounds of Chemical Formula 2, Chemical Formula 6, Chemical Formula 7, and Chemical Formula 14 obtained in Synthesis Examples 1 to 4, and Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4 shown below, the 50% mass reduction temperature (T1) by atmospheric pressure TG-DTA (thermogravimetry-differential thermal analysis), the state at 25°C, and the melting point were evaluated as follows. [Chemical Structure] [Chemical Structure] [Chemical Structure] [Chemical Structure] For Comparative Compound 4, the abbreviation "nBu" refers to the normal butyl group.

[0105] (1) Atmospheric pressure TG-DTA evaluation Using TG-DTA, under atmospheric pressure, the Ar flow rate was set to 100 mL / min, the heating rate was set to 10°C / min, the scanning temperature range was set to 30°C to 600°C, and the 50% mass reduction temperature (T1) of each of the compounds of Chemical Formula 2, Chemical Formula 6, Chemical Formula 7, and Chemical Formula 14 obtained in Synthesis Examples 1 to 4, and Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4 was measured, and the results are shown in Table 1 below. (2) Melting point evaluation For each of the compounds of Chemical Formula 2, Chemical Formula 6, Chemical Formula 7, and Chemical Formula 14 obtained in Synthesis Examples 1 to 4, and Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4, the state of the compound at 25°C was observed with the naked eye, and the melting point of the substance that was solid at 25°C was measured. The results are shown in Table 1 below. [Table 1]

[0106] From the results in Table 1, it was confirmed that all of the compounds of Chemical Formula 2, Chemical Formula 6, Chemical Formula 7, and Chemical Formula 14 are compounds with a normal pressure TG-DTA mass 50% reduction temperature (T1) of about 215°C or lower and a relatively high vapor pressure. Also, it was confirmed that all of the compounds of Chemical Formula 2, Chemical Formula 6, Chemical Formula 7, and Chemical Formula 14 are liquids at 25°C and have a melting point lower than 25°C. On the other hand, it was confirmed that each of Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4 has a relatively high melting point of 115°C or higher. Comparative Compound 1 and Comparative Compound 3 have a normal pressure TG-DTA mass 50% reduction temperature (T1) of around 180°C, are similar to the compounds according to the present invention, and have a relatively high vapor pressure. However, it was confirmed that their melting points are as high as 205°C or higher.

[0107] <<Evaluation Examples 5 to 8 and Comparative Evaluation Examples 5 to 8 (Metal-Containing Film Formation)>> Next, each of the compounds of Chemical Formula 2, Chemical Formula 6, Chemical Formula 7, and Chemical Formula 14 obtained in Synthesis Examples 1 to 4, and Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4 was used as a raw material, and a niobium nitride film or a tantalum nitride film was formed on a silicon substrate using the vapor deposition apparatus shown in Figure 3A.

[0108] The ALD process conditions for forming the niobium nitride film or the tantalum nitride film are as follows. (Conditions) Reaction temperature (substrate temperature): 250°C Reactive gas: Ammonia gas (Process) Under the conditions as described above, a series of processes (1) to (4) as follows were repeated 150 cycles as one cycle. Process (1): A step of introducing the vaporized raw material into the chamber under the conditions of a heating temperature of 90 °C of the raw material container and an internal pressure of 100 Pa of the raw material container, and depositing it for 30 seconds at a pressure of 100 Pa in the chamber. Process (2): A step of removing unreacted raw materials by Ar purge for 10 seconds. Process (3): A step of supplying a reactive gas and reacting it for 30 seconds at a chamber pressure of 100 Pa. Process (4): A step of removing unreacted raw materials by Ar purge for 10 seconds.

[0109] The thickness of each of the thin films obtained in the above processes was measured by the X-ray reflectivity method, the compound of each of the thin films obtained by the X-ray diffraction method was confirmed, and the carbon content of each of the thin films obtained by the X-ray photoelectron spectroscopy was measured, and the results are shown in Table 2 below.

Table 2

[0110] In the results of Table 2, among the thin films obtained by the ALD method, the thin films obtained from Comparative Compound 2 and Comparative Compound 4 each had a carbon content of 6 atomic % or more. On the other hand, the thin films obtained from the compounds of Chemical Formula 2, Chemical Formula 6, Chemical Formula 7, and Chemical Formula 14 were 0.1 atomic % or less, which is the detection limit, and it was confirmed that they were high-quality thin films. Further, as a result of evaluating the thin film thickness obtained after performing the ALD process for 150 cycles, in the cases of Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4, they were each 3 nm or less, while the thin films obtained from the compounds of Chemical Formula 2, Chemical Formula 6, Chemical Formula 7, and Chemical Formula 14 were 5.0 nm or more, and it was confirmed that they were excellent in the productivity of the thin film forming process. As confirmed from the above evaluation examples, the organometallic addition compound according to the embodiment of the present invention has a low melting point and a high vapor pressure, and can enhance the productivity of thin film formation when used as a raw material for thin film formation by an ALD process or a CVD process.

[0111] Note that the present invention is not limited to the above-described embodiments and examples. Various modifications can be made without departing from the technical scope of the present invention.

Explanation of Reference Numerals

[0112] Evaporation apparatuses 200A, 200B, 200C, 200D Fluid transfer section 210 Raw material container 212 Heater 214 Inflow lines 222, 262, 264, 266, 268 Outflow line 224 Thin film formation section 250 Susceptor 252 Reaction chamber 254 Shower head 256 Vaporizer 258 Exhaust system 270 Exhaust line 272 Vacuum pump 274 Trap 276 Bypass line 278 Automatic pressure controller 280 High-frequency power supply 292 RF matching system 294 Substrate 310 Dielectric film 360 Capacitor 370 Lower electrode of LE MFCs M1 to M5 Upper electrode of UE Valves V1 to V8

Claims

1. An organometallic addition compound characterized by being represented by the general formula I shown below. 【Chemical I】 (In the general formula I, R １ , R ２ , and R ３ are each independently a trifluoromethyl group, a trifluoroethyl group, a hexafluoroisopropyl group, or a nonafluorotert-butyl group, M is a niobium atom, a tantalum atom, or a vanadium atom, X is a halogen atom, m is an integer from 3 to 5, n is 1 or 2.)

2. In the general formula I, M is a niobium atom or a tantalum atom, The organometallic addition compound according to claim 1, wherein X is a fluorine atom or a chlorine atom.

3. In the general formula I, m is 5, The organometallic addition compound according to claim 1, wherein n is 1.

4. The organometallic addition compound according to claim 1, wherein the compound of the general formula I is liquid at a temperature of 20°C to 28°C.

5. A method for manufacturing an integrated circuit element, comprising forming a metal-containing film on a substrate using an organometallic addition compound of the general formula I shown below. 【Chemical I】 (In the general formula I, R １ , R ２ , and R ３ are each independently a trifluoromethyl group, a trifluoroethyl group, a hexafluoroisopropyl group, or a nonafluorotert-butyl group, M is a niobium atom, a tantalum atom, or a vanadium atom, X is a halogen atom, m is an integer from 3 to 5, n is 1 or 2.)

6. The method for manufacturing an integrated circuit element according to claim 5, wherein the organometallic addition compound is liquid at a temperature of 20°C to 28°C.

7. In the general formula I, M is a niobium atom or a tantalum atom, The method for manufacturing an integrated circuit element according to claim 5, wherein X is a fluorine atom or a chlorine atom.

8. In the general formula I, m is 5, The method for manufacturing an integrated circuit element according to claim 5, wherein n is 1.

9. The step of forming the metal-containing film includes supplying the organometallic addition compound of the general formula I onto the substrate And supplying a reactive gas onto the substrate, The method for manufacturing an integrated circuit element according to claim 5.

10. The reactive gas is NH ３ , N ２ plasma, an organic amine compound, a hydrazine compound, or a combination thereof, according to claim 9, a method for manufacturing an integrated circuit device, characterized in that it is selected from.

11. The reactive gas is O ２ , O ３ , O ２ plasma, H ２ O, NO ２ , NO, N ２ O (nitrous oxide), CO, CO ２ , H ２ O ２ , HCOOH, CH ３ COOH, (CH ３ CO) ２ O, alcohol, peroxide, sulfur oxide, or a combination thereof, and the method for manufacturing an integrated circuit element according to claim 9, characterized in that it is selected from the group consisting of these substances.

12. The reactive gas is H ２ The method for manufacturing an integrated circuit device according to claim 9, characterized in that it is so.

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