TWI871531B - Organometallic adduct compound and method of manufacturing integrated circuit device by using the same - Google Patents

Abstract

An organometallic adduct compound and a method of manufacturing an integrated circuit device, the organometallic adduct compound being represented by General Formula (I):

Description

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

[Cross reference to related applications]

This application is based on and claims priority from Korean Patent Application No. 10-2021-0123465 filed on September 15, 2021 with the Korean Intellectual Property Office, and the disclosure of the Korean patent application is hereby incorporated by reference in its entirety.

Embodiments relate to an organometallic adduct compound and a method of fabricating an integrated circuit device using the organometallic adduct compound.

Due to the development of electronic technology, semiconductor devices have been rapidly scaled down in recent years, and therefore, the size of patterns constituting electronic devices has been more finely determined.

The embodiments can be achieved by providing an organometallic adduct compound represented by the general formula (I):

General formula (I)

Wherein, in the general formula (I), R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C5 straight chain alkyl group, a substituted or unsubstituted C3 to C5 branched chain alkyl group, a substituted or unsubstituted C2 to C5 straight chain alkenyl group or a substituted or unsubstituted C3 to C5 branched chain alkenyl group, X is a halogen atom, and M is a niobium atom or a tantalum atom.

The embodiments can be achieved by providing a method for manufacturing an integrated circuit device, the method comprising forming a metal-containing film on a substrate using an organometallic adduct compound represented by the general formula (I):

General formula (I)

Wherein, in the general formula (I), R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C5 straight chain alkyl group, a substituted or unsubstituted C3 to C5 branched chain alkyl group, a substituted or unsubstituted C2 to C5 straight chain alkenyl group or a substituted or unsubstituted C3 to C5 branched chain alkenyl group, X is a halogen atom, and M is a niobium atom or a tantalum atom.

The term "substrate" used herein may refer to the substrate itself, or may refer to a stack structure including the substrate and a specific layer or film or similar element formed on the surface of the substrate. In addition, the term "surface of the substrate" used herein may refer to the exposed surface of the substrate itself, or may refer to the outer surface of a specific layer or film or similar element formed on the substrate. The abbreviation "Me" used herein refers to a methyl group, the abbreviation "Et" refers to an ethyl group, the abbreviation "nPr" refers to an n-propyl group, and the abbreviation "tBu" refers to a tert-butyl group (1,1-dimethylethyl). The term "room temperature" or "ambient temperature" used herein refers to a temperature ranging from about 20°C to about 28°C, and may vary with the season. The term "or" used in this document is not an exclusive term. For example, "A or B" will include A, B, or A and B.

The organic metal addition compound according to the embodiment may have a structure in which a pyridine derivative is bonded to a coordinated metal compound in the form of an adduct. The organic metal addition compound according to the embodiment may be represented by the general formula (I). General formula (I)

In the general formula (I), R ¹ , R ² , R ³ , R ⁴ and R ⁵ may each independently be or include, for example, a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C5 straight chain alkyl group, a substituted or unsubstituted C3 to C5 branched chain alkyl group, a substituted or unsubstituted C2 to C5 straight chain alkenyl group or a substituted or unsubstituted C3 to C5 branched chain alkenyl group.

X may be, for example, a halogen atom.

M may be, for example, a niobium atom or a tantalum atom. In the general formula (I), the arrows may represent coordinate bonds or dative bonds.

In one embodiment, in the general formula (I), R ¹ , R ² , R ³ , R ⁴ and R ⁵ may each independently be, for example, a fluorine atom, a chlorine atom, a bromine atom, 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 t-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a t-pentyl group, a neopentyl group, a 3-pentyl group, a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a trifluoroethyl group, a trifluoropropyl group, a trifluoroisopropyl group, a hexafluoroisopropyl group, a dimethyltrifluoroethyl group, a (trifluoromethyl)tetrafluoroethyl group or a nonafluorot-butyl group.

In one embodiment, in the general formula (I), X may be, for example, a fluorine atom, a chlorine atom or a bromine atom. In one embodiment, when X is a fluorine atom or a chlorine atom, the organometallic addition compound according to the general formula (I) may have a relatively low melting point and a relatively high vapor pressure.

In one embodiment, in the general formula (I), at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may include, for example, a halogen atom.

In one embodiment, in the general formula (I), at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be, for example, a fluorine atom, a C1 to C5 straight chain alkyl group substituted with a fluorine atom, a C3 to C5 branched chain alkyl group substituted with a fluorine atom, a C2 to C5 straight chain alkenyl group substituted with a fluorine atom, or a C3 to C5 branched chain alkenyl group substituted with a fluorine atom.

In one embodiment, in the general formula (I), one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be, for example, a hydrogen atom, another of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be, for example, a fluorine atom, and yet another of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be, for example, a C1 to C5 straight-chain alkyl group substituted with a fluorine atom, a C3 to C5 branched-chain alkyl group substituted with a fluorine atom, a C2 to C5 straight-chain alkenyl group substituted with a fluorine atom, or a C3 to C5 branched-chain alkenyl group substituted with a fluorine atom.

In one embodiment, in the general formula (I), at least one of R ¹ and R ² may be, for example, a fluorine atom.

In one embodiment, in the general formula (I), M may be, for example, a niobium atom, and at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be, for example, a halogen atom.

In one embodiment, in the general formula (I), X may be, for example, a fluorine atom or a chlorine atom, M may be, for example, a niobium atom, and at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be, for example, a fluorine atom.

In one embodiment, in the general formula (I), M may be, for example, a niobium atom, and at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be, for example, a fluorine atom, a C1 to C5 straight chain alkyl group substituted with a fluorine atom, a C3 to C5 branched chain alkyl group substituted with a fluorine atom, a C2 to C5 straight chain alkenyl group substituted with a fluorine atom, or a C3 to C5 branched chain alkenyl group substituted with a fluorine atom.

In one embodiment, in the general formula (I), M may be, for example, a titanium atom, and at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be, for example, a fluorine atom, a C1 to C5 straight chain alkyl group substituted with a fluorine atom, a C3 to C5 branched chain alkyl group substituted with a fluorine atom, a C2 to C5 straight chain alkenyl group substituted with a fluorine atom, or a C3 to C5 branched chain alkenyl group substituted with a fluorine atom.

In one embodiment, in the general formula (I), X may be, for example, a fluorine atom or a chlorine atom, and at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may include, for example, a fluorine atom.

In one embodiment, in the general formula (I), X may be, for example, a fluorine atom, and at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be, for example, a fluorine atom, a C1 to C5 straight chain alkyl group substituted with a fluorine atom, a C3 to C5 branched chain alkyl group substituted with a fluorine atom, a C2 to C5 straight chain alkenyl group substituted with a fluorine atom, or a C3 to C5 branched chain alkenyl group substituted with a fluorine atom.

In one embodiment, in the general formula (I), M may be, for example, a niobium atom or a tantalum atom, and X may be, for example, a fluorine atom or a chlorine atom.

In one embodiment, in order to form a high-quality thin film with excellent productivity, in the general formula (I), when M is a niobium atom, at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be, for example, a halogen atom, a C1 to C3 alkyl group, a C2 to C3 alkenyl group or a C1 to C3 alkyl group substituted with a fluorine atom. In one embodiment, in the general formula (I), when M is a niobium atom, at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be, for example, a fluorine atom, a chlorine atom, a methyl group, an ethyl group, a trifluoromethyl group or a trifluoroethyl group.

In one embodiment, in order to form a high-quality thin film with excellent productivity, in the general formula (I), when M is a niobium atom, two to four of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may each be, for example, a hydrogen atom, and one to three of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may each be, for example, a halogen atom, a C1 to C5 alkyl group, a C2 to C5 alkenyl group or a C1 to C5 alkyl group substituted with a fluorine atom. In one embodiment, three or four of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may each be, for example, a hydrogen atom, and one or two of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may each be, for example, a halogen atom, a C1 to C5 alkyl group, a C2 to C5 alkenyl group, or a C1 to C5 alkyl group substituted with a fluorine atom. In one embodiment, R ¹ , R ³ , R ⁴ and R ⁵ may each be, for example, a hydrogen atom, and R ² may be, for example, a halogen atom, a C1 to C5 alkyl group, a C2 to C5 alkenyl group, or a C1 to C5 alkyl group substituted with a fluorine atom. In one embodiment, R ² , R ³ and R ⁴ may each be, for example, a hydrogen atom, and R ¹ and R ⁵ may each be, for example, a halogen atom, a C1 to C5 alkyl group, a C2 to C5 alkenyl group, or a C1 to C5 alkyl group substituted with a fluorine atom.

The organic metal addition compound according to the embodiment may have a structure in which a pyridine derivative is bonded to a coordinated metal compound in the form of an adduct, and may provide excellent thermal stability. Therefore, when the organic metal addition compound according to the embodiment is used as a precursor of a metal when a metal-containing film is formed by a chemical vapor deposition (CVD) process or an atomic layer deposition (ALD) process, the organic metal addition compound according to the embodiment may be stably transported without being decomposed due to heat during its transport from a storage container to a reaction chamber. In addition, when the organic metal addition compound according to the embodiment is supplied to a deposition reaction chamber for forming a metal-containing film, the organic metal addition compound may be easily decomposed due to the process temperature in the reaction chamber, and thus may not affect the surface reaction for forming the metal-containing film. Therefore, when the metal-containing film is formed using the organic metal addition compound according to the embodiment, the phenomenon that undesirable foreign matter (e.g., carbon residue) remains in the metal-containing film to be formed may be suppressed, and the organic metal addition compound may be suitably used as a source material for forming a low-resistance metal-containing film with good quality, and the productivity of the manufacturing process of the integrated circuit device may be improved.

Examples of the organometallic addition compound according to the embodiment can be represented by the following Formulae 1 to 456.

The organometallic adduct compound according to the embodiment can be synthesized using a suitable reaction. In one embodiment, NbF ₅ (V), NbCl ₅ (V), TaF ₅ (V) or TaCl ₅ (V) can be reacted with a pyridine compound (having a structure corresponding to the final structure to be synthesized) in a dichloromethane solvent, and then, the obtained solution can be subjected to solvent removal and purification by distillation, thereby obtaining a niobium compound or a tantalum compound represented by the general formula (I).

The organometallic addition compound according to the embodiment may be used as a source material suitable for a CVD process or an ALD process.

FIG. 1 is a flow chart of a method for manufacturing an integrated circuit device according to an embodiment.

1 , in process P10, a substrate may be prepared.

The substrate may include, for example, silicon, ceramic, glass, metal, metal nitride, or a combination thereof. The ceramic may include, for example, silicon nitride, titanium nitride, tantalum nitride, titanium oxide, niobium oxide, zirconium oxide, tantalum oxide, or a combination thereof. Each of the metal and the metal nitride may include, for example, Ti, Ta, Co, Ru, Zr, Hf, La, or a combination thereof. The surface of the substrate may have a flat shape, a spherical shape, a fibrous shape, or a scale-like shape. In one embodiment, the surface of the substrate may have a three-dimensional structure, such as a trench structure or a similar structure.

In one embodiment, the substrate may have a configuration as described below with respect to substrate 310 with reference to FIG. 4A .

In the process P20 shown in FIG. 1 , a metal-containing film may be formed on a substrate using a source material for forming a metal-containing film, wherein the source material includes the organic metal addition compound represented by the general formula (I).

The source material for forming the metal-containing film may include the organic metal addition compound according to the embodiment. In one embodiment, the source material for forming the metal-containing film may include at least one of the organic metal addition compounds represented by, for example, Formula 1 to Formula 324.

The source material used for the formation of the metal-containing film may vary depending on the film to be formed. In one embodiment, the metal-containing film to be formed may include a niobium-containing film or a tantalum-containing film. When forming a niobium-containing film, the organic metal addition compound according to the general formula (I) (wherein M is a niobium atom) may be used as a source material for the formation of the metal-containing film. When forming a tantalum-containing film, the organic metal addition compound according to the general formula (I) (wherein M is a tantalum atom) may be used as a source material for the formation of the metal-containing film.

In one embodiment, when the metal-containing film to be formed contains only niobium atoms or tantalum atoms as metal atoms, the source material used for forming the metal-containing film may not include other metal compounds and semi-metal compounds except the niobium compound or tantalum compound represented by the general formula (I).

In one embodiment, the metal-containing film to be formed may further contain another metal in addition to niobium or tantalum. In one embodiment, when the metal-containing film to be formed is a film containing another metal or semimetal in addition to niobium or tantalum, in addition to the organic metal addition compound according to the embodiment, the source material for forming the metal-containing film may also include a compound containing the desired metal or semimetal (hereinafter referred to as "another precursor"). In one embodiment, in addition to the organic metal addition compound according to the embodiment, the source material for forming the metal-containing film may further include an organic solvent or a nucleophilic reagent.

In order to form a metal-containing film according to process P20 shown in FIG1 , a CVD process or an ALD process may be used. The source material for metal-containing film formation including the organometallic adduct compound according to the embodiment may be suitable for use in a chemical deposition process such as a CVD process or an ALD process.

When the source material for metal-containing film formation is used in a chemical vapor deposition process, the composition of the source material for metal-containing film formation can be appropriately selected according to the method of transporting the source material. The method of transporting the source material may include, for example, a vapor transport method or a liquid transport method. In the vapor transport method, the source material can be made into a vapor state by heating or depressurizing the source material in a container (hereinafter referred to as a "source material container") in which the source material for metal-containing film formation is stored to vaporize the source material, and the source material in the vapor state can be introduced into a chamber (hereinafter referred to as a "deposition reaction unit") in which a substrate is arranged together with a carrier gas (such as argon, nitrogen, helium or the like) used as needed. In the liquid delivery method, the source material may be delivered to a vaporization chamber in a liquid state or a solution state, and vapor may be formed by heating and/or compressing the source material in the vaporization chamber, and then the vapor may be introduced into the chamber.

When a vapor delivery method is used to form a metal-containing film according to process P20 shown in FIG. 1 , the organometallic adduct compound represented by general formula (I) itself can be used as a source material for metal-containing film formation. When a liquid delivery method is used to form a metal-containing film according to process P20 shown in FIG. 1 , the organometallic adduct compound represented by general formula (I) itself or a solution in which the organometallic adduct compound represented by general formula (I) is dissolved in an organic solvent can be used as a source material for metal-containing film formation. The source material for metal-containing film formation may further include another precursor, a nucleophilic reagent, or the like.

In one embodiment, in order to form a metal-containing film according to the method for manufacturing an integrated circuit device according to the embodiment, a multi-component chemical deposition method may be used. In the multi-component chemical deposition method, a method in which each component of the source material for metal-containing film formation is independently vaporized and supplied (which may be referred to as a "single source method" hereinafter) may be used, or a method in which a mixed source material is obtained by mixing a plurality of components in a desired composition in advance (which may be referred to as a "cocktail source method" hereinafter) may be used. When the cocktail source method is used, a mixture of the organometallic adduct compound according to the embodiment and another precursor or a mixed solution in which the mixture is dissolved in an organic solvent may be used as a source material for metal-containing film formation. The mixture or the mixed solution may further contain a nucleophilic reagent.

The organic solvent may include a suitable organic solvent. In one embodiment, the organic solvent may include, for example: acetates, such as ethyl acetate, butyl acetate or methoxyethyl acetate; ethers, such as tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether or dibutyl ether; ketones, such as methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone or methyl cyclohexanone; hydrocarbons, such as hexane, cyclohexane, 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane or 1,4-dicyanobenzene; pyridine; lutidine; or similar solvents. The organic solvents described above as examples may be used alone or as a mixed solvent of at least two of them, taking into account the solubility of the solute, the use temperature and its boiling point, flash point or the like.

When the organic solvent is included in the source material for metal-containing film formation including the organic metal addition compound according to the embodiment, the organic metal addition compound and another precursor may be present in the organic solvent in a total amount of about 0.01 mol/L to about 2.0 mol/L (e.g., about 0.05 mol/L to about 1.0 mol/L). In one embodiment, when the source material used for the formation of the metal-containing film does not contain other metal compounds or semi-metal compounds in addition to the organic metal addition compound according to the embodiment, the total amount specified above is the amount of the organic metal addition compound, and when the source material used for the formation of the metal-containing film also contains another metal compound or semi-metal compound (for example, another precursor) in addition to the organic metal addition compound according to the embodiment, the total amount specified above is the sum of the amount of the organic metal addition compound and the amount of the other precursor.

When a metal-containing film is formed using a multicomponent chemical deposition method according to a method of manufacturing an integrated circuit device, another precursor that can be used together with the organometallic adduct compound according to an embodiment may include other suitable precursors used as source materials for metal-containing film formation.

In one embodiment, another precursor that can be used to form a metal-containing film according to the method of manufacturing an integrated circuit device may include an organic coordination compound, such as an alcohol compound, a diol compound, a β-diketone compound, a cyclopentadiene compound, an organic amine compound, a silicon compound, or a metal compound.

The other precursor may include, for example, lithium (Li), sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti), zirconium (Zr), humus (Hf), vanadium (V), 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), aluminium (Al), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), yttrium (Y), la, ce, pr, neodymium (Nd), pm, sm, eu, gadillium (Gd), tb, dynamite (Dy), ho, erbium (Er), tm, yttrium (Yb), ruthenium (Ru) or lumen (Lu).

Examples of alcohol compounds having an organic ligand of another precursor may include: alkyl alcohols such as methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, isobutanol, t-butanol, pentanol, isopentanol and t-pentanol; 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 and 3-methoxy-1,1-dimethylpropanol; and dialkylaminoalcohols such as dimethylaminoethanol, ethylmethylaminoethanol, diethylaminoethanol, dimethylamino-2-pentanol, ethylmethylamino-2-pentanol, dimethylamino-2-methyl-2-pentanol, ethylmethylamino-2-methyl-2-pentanol and diethylamino-2-methyl-2-pentanol.

Examples of the diol compound that can be used as the organic coordination compound of another precursor may include 1,2-ethanediol, 1,2-propylene glycol, 1,3-propylene glycol, 2,4-hexanediol, 2,2-dimethyl-1,3-propylene glycol, 2,2-diethyl-1,3-propylene glycol, 1,3-butylene glycol, 2,4-butylene glycol, 2,2-diethyl-1,3-butylene glycol, 2-ethyl-2-butyl-1,3-propylene glycol, 2,4-pentanediol, 2-methyl-1,3-propylene glycol, 2-methyl-2,4-pentanediol, 2,4-hexanediol, and 2,4-dimethyl-2,4-pentanediol.

Examples of the β-diketone compound that can be used as the organic coordination compound of another precursor may include alkyl-substituted β-diketones such as 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, 2,6-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-dimethyl nonane-4,6-dione, 2-methyl-6-ethyldecane-3,5-dione and 2,2-dimethyl-6-ethyldecane-3,5-dione; fluorine-substituted alkyl β-diketones, such as 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 and 1,3-diperfluorohexylpropane-1,3-dione; and ether-substituted β-diketones, such as 1,1,5,5-tetramethyl-1-methoxyhexane-2,4-dione, 2,2,6,6-tetramethyl-1-methoxyheptane-3,5-dione and 2,2,6,6-tetramethyl-1-(2-methoxyethoxy)heptane-3,5-dione.

Examples of the cyclopentadiene compound that can be used as the organic coordination compound of another precursor may include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, sec-butylcyclopentadiene, isobutylcyclopentadiene, tert-butylcyclopentadiene, dimethylcyclopentadiene, and tetramethylcyclopentadiene.

Examples of the organic amine compound that can be used as the organic coordination compound of another precursor may include methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, ethylmethylamine, propylmethylamine, and isopropylmethylamine.

The other precursor may be a suitable precursor, and a suitable method may be used to manufacture the other precursor. In one embodiment, when an alcohol compound is used as an organic ligand, the precursor may be manufactured by reacting an inorganic salt of the above-mentioned element or a hydrate thereof with an alkali metal alkoxide of the alcohol compound. Examples of the inorganic salt of the above-mentioned element or a hydrate thereof may include metal halides, acetic acid, and similar materials. Examples of alkali metal alkoxides may include sodium alkoxides, lithium alkoxides, potassium alkoxides, and similar materials.

When the single source method is used, a compound having a thermal decomposition and/or oxidative decomposition behavior similar to that of the organometallic adduct compound according to the embodiment may be used as the other precursor. When the cocktail source method is used, a compound having a thermal decomposition and/or oxidative decomposition behavior similar to that of the organometallic adduct compound according to the embodiment and not deteriorating due to a chemical reaction or the like when mixed may be used as the other precursor.

When a metal-containing film is formed according to the method for manufacturing an integrated circuit device according to an embodiment, the source material used for the formation of the metal-containing film may include a nucleophile. The nucleophile may impart stability to the niobium compound or tantalum compound according to the embodiment and/or the other precursor. Nucleophilic agents may include, for example, glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether; crown ethers such as 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8 or 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 or triethoxytriethyleneamine; cyclic polyamines such as tetramethylethylenetriamine, triethylenetetramine ... a cyclotetradecane (cyclam) or a cyclododecane (cyclen); a heterocyclic compound such as pyridine, pyrrolidine, piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, oxazole, thiazole or oxathiolane; a β-ketoester such as methyl acetylacetate, ethyl acetylacetate or ethyl 2-methoxyacetylacetate; or a β-diketone such as acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione or dipivaloylmethane. The nucleophilic agent may be present in an amount of about 0.1 mol to about 10 mol (e.g., about 1 mol to about 4 mol) based on 1 mol of the total amount of the precursor.

It may be desirable to suppress as much as possible the amount of metal element impurities, halogen impurities (e.g., chlorine impurities or similar impurities), and organic impurities in a source material for metal-containing film formation (which is used to form a metal-containing film according to a method of manufacturing an integrated circuit device according to an embodiment). In one embodiment, each of the metal element impurities may be present in an amount of about 100 parts per billion (ppb) (e.g., by weight) or less than 100 ppb in the source material for metal-containing film formation. In one embodiment, each of the metal element impurities may be present in an amount of about 10 ppb or less in the metal element impurities, and the metal element impurities may be present in a total amount of about 1 parts per million (ppm) or less (e.g., about 100 ppb or less). In one embodiment, when a thin film used as a gate insulating film, a gate conductive film, or a barrier film of a large-scale integrated circuit (LSI) is formed, the amount of alkali metal elements and alkali earth metal elements that affect the electrical properties of the obtained thin film may be minimized. In one embodiment, the halogen impurities may be present in the source material used for metal-containing film formation in an amount of about 100 ppm or less (eg, about 10 ppm or less or about 1 ppm or less).

The organic impurities may be present in a total amount of about 500 ppm or less (eg, about 50 ppm or less or about 10 ppm or less) in the source material used for metal-containing film formation.

When water is present in the source material used for metal-containing film formation, the water may cause particles to be generated in the source material, or may cause particles to be generated during film formation. In one embodiment, the precursor, organic solvent, and nucleophilic reagent may be subjected to water removal before use. Water may be present in an amount of about 10 ppm or less (e.g., about 1 ppm or less) in each of the precursor, organic solvent, and nucleophilic reagent.

When a metal-containing film is formed according to a method for manufacturing an integrated circuit, in order to reduce particle contamination in the metal-containing film to be formed, the amount of particles in the source material used for the metal-containing film formation may be minimized. In one embodiment, when particle measurement for a liquid phase is performed by a light scattering type particle detector, particles larger than 0.3 microns may be present in the number of 100 or less in 1 ml of liquid of the source material used for the metal-containing film formation, and particles larger than 0.2 microns may be present in the number of 1000 or less (e.g., 100 or less) in the 1 ml of liquid of the source material.

In process P20 shown in FIG. 1 , in order to form a metal-containing film using a source material for forming a metal-containing film, process P20 may include, for example: a process of introducing the source material for forming a metal-containing film into a deposition reaction unit where a substrate is located by vaporizing the source material for forming a metal-containing film and then forming a precursor film on the substrate by depositing the source material for forming a metal-containing film on the surface of the substrate; and a process of forming a metal-containing film containing niobium atoms or tantalum atoms on the surface of the substrate by reacting the precursor film with a reaction gas.

In order to introduce the source material for metal-containing film formation into the deposition reaction unit by vaporizing the source material, the above-mentioned gas delivery method, liquid delivery method, single source method or cocktail source method may be used.

The reaction gas is a gas that reacts with the precursor film. In one embodiment, the reaction gas may include, for example, an oxidizing gas or a nitrifying gas.

The oxidizing gas may include, for example, _O2 , _O3 , _O2 plasma, _H2O , _NO2 , NO, _N2O (nitrous oxide), CO, _CO2 , _H2O2 , _HCOOH , _CH3COOH , ( _CH3CO ) _2O , alcohols, peroxides, sulfur oxides, or combinations thereof.

The nitrating gas may include, for example, NH ₃ , N ₂ plasma, an organic amine compound (eg, monoalkylamine, dialkylamine, trialkylamine, or alkylenediamine), a hydrazine compound, or a combination thereof.

In the process P20 shown in FIG1 , when a metal oxide film containing niobium atoms or tantalum atoms is formed, the oxidizing gas may be used as a reactive gas. In the process P20 shown in FIG1 , when a metal nitride film containing niobium atoms or tantalum atoms is formed, the nitrifying gas may be used as a reactive gas.

In one embodiment, in order to form a metal-containing film containing niobium atoms or tantalum atoms in process P20 shown in Figure 1, a thermal CVD process in which a source gas including the organic metal addition compound according to the embodiment and a reaction gas are reacted using only heat to form a thin film, a plasma CVD process using heat and plasma for reaction, an optical CVD process using heat and light for reaction, an optical plasma CVD process using heat, light and plasma for reaction, or an ALD process can be used.

When forming a metal-containing film according to process P20 shown in FIG1 , a reaction temperature (substrate temperature), reaction pressure, deposition rate or similar parameters may be appropriately selected according to the thickness and type of the desired metal-containing film. The reaction temperature may be in the range of room temperature or ambient temperature to about 600° C. (e.g., about 400° C. to about 550° C.), which is sufficient for the reaction of the source material used for metal-containing film formation.

When forming a metal-containing film according to process P20 shown in FIG. 1 , when an ALD process is used, the thickness of the metal-containing film can be adjusted by adjusting the number of cycles of the ALD process. When the metal-containing film is formed on a substrate using the ALD process, the ALD process may include: for example, a source material introduction process, in which vapor formed by vaporizing a source material used for metal-containing film formation (which includes an organic metal adduct compound according to an embodiment) is introduced into a deposition reaction unit; a precursor film formation process, in which a precursor film is formed on the surface of the substrate using the vapor; an exhaust process, in which unreacted source gas remaining in a reaction space above the substrate is exhausted; and a process of forming a metal-containing film on the surface of the substrate by chemically reacting the precursor film with the reaction gas.

In one embodiment, the process of vaporizing the source material for metal-containing film formation may be performed in a source material container or a vaporization chamber. The process of vaporizing the source material for metal-containing film formation may be performed at about 0° C. to about 200° C. When the source material for metal-containing film formation is vaporized, the pressure in the source material container or the vaporization chamber may be about 1 Pa to about 10,000 Pa.

FIG2 is a flow chart of an exemplary method for forming a metal-containing film according to a method for manufacturing an integrated circuit device according to an embodiment. The method for forming a metal-containing film by an ALD process according to process P20 shown in FIG1 will be described with reference to FIG2.

2 , in process P21 , a source gas including an organic metal adduct compound having a structure of formula (I) may be gasified.

In one embodiment, the source gas may include the above-mentioned source material for metal-containing film formation. The process of vaporizing the source gas may be performed at about 0° C. to about 200° C. When the source gas is vaporized, the pressure in the source material container or the vaporization chamber may be about 1 Pa to about 10,000 Pa.

In process P22, a metal source adsorption layer including niobium atoms or tantalum atoms may be formed on the substrate by supplying the source gas vaporized according to process P21 onto the substrate. In one embodiment, the reaction temperature may be in a range from room temperature to about 600° C. (e.g., about 400° C. to about 550° C.). The reaction pressure may be about 1 Pa to about 10,000 Pa (e.g., about 10 Pa to about 1,000 Pa).

An adsorption layer including a chemisorbed layer and a physisorbed layer of the vaporized source gas may be formed on the substrate by supplying the vaporized source gas onto the substrate.

In process P23 , unnecessary byproducts on the substrate may be removed by supplying a purge gas onto the substrate.

The purge gas may include, for example, an inert gas (such as Ar, He, or Ne), N ₂ gas, or the like.

In one embodiment, exhaust can be performed by depressurizing the reaction space where the substrate is located rather than by a purge process. In one embodiment, to depressurize, the pressure of the reaction space can be maintained at about 0.01 Pa to about 300 Pa (e.g., about 0.01 Pa to about 100 Pa).

In one embodiment, a process of heating the substrate on which the metal source adsorption layer including niobium atoms or tantalum atoms is formed or heat-treating the reaction chamber in which the substrate is accommodated may be further performed. The heat treatment may be performed at a temperature ranging from room temperature to about 600° C. (e.g., about 400° C. to about 550° C.).

In process P24, a metal-containing film may be formed in atomic layer units by supplying a reaction gas onto a metal source adsorption layer formed on a substrate.

In one embodiment, a metal oxide film including niobium atoms or tantalum atoms may be formed on a substrate, and the reaction gas may be an oxidizing gas, such as _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 one embodiment, a metal nitride film including niobium atoms or tantalum atoms may be formed on a substrate, and the reaction gas may be, for example, NH ₃ , N ₂ plasma, an organic amine compound (such as monoalkylamine, dialkylamine, trialkylamine, or alkylenediamine), a hydrazine compound, and a combination thereof.

During process P24, the reaction space may be maintained at a temperature ranging from room temperature to about 600° C. (e.g., about 400° C. to about 550° C.) so that the metal source adsorption layer including niobium atoms or tantalum atoms can fully react with the reaction gas. During process P24, the pressure of the reaction space may be about 1 Pa to about 10,000 Pa (e.g., about 10 Pa to about 1,000 Pa).

During process P24, the reaction gas may be subjected to plasma treatment, wherein a radio frequency (RF) output in the plasma treatment may be about 0 watts to about 1,500 watts (eg, about 50 watts to about 600 watts).

In process P25, unnecessary byproducts on the substrate are removed by supplying a purge gas onto the substrate.

The purge gas may include, for example, an inert gas (such as Ar, He, or Ne), N ₂ gas, or the like.

In process P26, processes P21 to P25 may be repeated until a metal-containing film having a desired thickness is formed.

The thin film deposition process including a series of processes including processes P21 to P25 may be defined as one cycle, and the cycle may be repeated a plurality of times until a metal-containing film having a desired thickness is formed. In one embodiment, when performing the one cycle, unreacted gas may be exhausted from the reaction chamber by performing an exhaust process using a purge gas similar to process P23 or process P25, and then, a subsequent cycle may be performed.

In one embodiment, to help control the deposition rate of the metal-containing film, source material supply conditions (e.g., vaporization temperature or vaporization pressure of the source material), reaction temperature, reaction pressure, or similar parameters may be controlled. If the deposition rate of the metal-containing film is too high, the obtained metal-containing film may have degraded properties, and if the deposition rate of the metal-containing film is too low, productivity may be degraded. In one embodiment, the deposition rate of the metal-containing film may be about 0.01 nm/min to about 100 nm/min (e.g., about 0.1 nm/min to about 50 nm/min).

In the process of forming the metal-containing film, various suitable changes and modifications may be made to the metal-containing film.

In one embodiment, in order to form a metal-containing film on a substrate, the organometallic adduct compound having a structure of the general formula (I) and at least one of the other precursor, the reaction gas, the carrier gas, and the purge gas may be supplied to the substrate simultaneously or sequentially. A more detailed configuration of the other precursor, the reaction gas, the carrier gas, and the purge gas that may be supplied to the substrate simultaneously with the organometallic adduct compound having a structure of the general formula (I) is as described above.

In one embodiment, in the process of forming the metal-containing film described with reference to FIG. 2 , a reactive gas may be supplied onto the substrate between each of processes P21 to P25 .

3A to 3D are schematic diagrams of configurations of exemplary deposition apparatuses 200A, 200B, 200C, and 200D that may be used in a process of forming a metal-containing film in a method of manufacturing an integrated circuit device according to an embodiment.

Each of the deposition apparatuses 200A, 200B, 200C and 200D shown in FIGS. 3A to 3D may include a fluid delivery unit 210, a thin film forming unit 250, and an exhaust system 270. A deposition process of forming a thin film on a substrate W using a process gas supplied from a source material container 212 in the fluid delivery unit 210 is performed in the thin film forming unit 250. The exhaust system 270 is used to discharge gas that may remain after a reaction in the thin film forming unit 250 or to discharge reaction by-products.

The thin film forming unit 250 may include a reaction chamber 254 including a susceptor 252 supporting the substrate W. A shower head 256 for supplying a gas supplied from the fluid delivery unit 210 onto the substrate W may be installed in an upper end portion of the reaction chamber 254 .

The fluid delivery unit 210 may include an inflow line 222 and an outflow line 224, wherein the inflow line 222 is used to supply a carrier gas from the outside of each deposition device to the source material container 212, and the outflow line 224 is used to supply the source compound contained in the source material container 212 to the thin film forming unit 250. Valves V1 and V2 and mass flow controllers (MFCs) M1 and M2 may be installed on the inflow line 222 and the outflow line 224, respectively. The inflow line 222 and the outflow line 224 may be connected to each other via a bypass line 226. A valve V3 may be installed on the bypass line 226. The valve V3 may be pneumatically operated by an electric motor or other remotely controllable tool.

The source compound supplied from the source material container 212 may be supplied to the reaction chamber 254 via an inflow line 266 of the thin film forming unit 250, and the inflow line 266 is connected to the outflow line 224 of the fluid delivery unit 210. If necessary, the source compound supplied from the source material container 212 may be supplied to the reaction chamber 254 together with a carrier gas supplied via an inflow line 268. A valve V4 and an MFC M3 may be installed on the inflow line 268 through which the carrier gas flows.

The film forming unit 250 may include an inflow pipeline 262 for supplying a purge gas into the reaction chamber 254 and an inflow pipeline 264 for supplying a reaction gas into the reaction chamber 254. Valves V5 and V6 and MFCs M4 and M5 may be installed on the inflow pipelines 262 and 264, respectively.

The used process gas and waste reaction byproducts in the reaction chamber 254 may be exhausted to the outside of each deposition apparatus 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 installed on the exhaust line 272. The vacuum pump 274 may remove the process gas and waste reaction byproducts exhausted from the reaction chamber 254.

A trap 276 may be installed on the exhaust line 272 at the upstream side of the vacuum pump 274. The trap 276 may capture reaction byproducts generated by, for example, process gases that are not completely reacted in the reaction chamber 254, and thus prevent the reaction byproducts from flowing to the vacuum pump 274 at the downstream side of the trap 276.

The trap 276 installed on the exhaust line 272 can capture foreign matter such as reaction byproducts generated by the reaction between process gases, and thus can prevent the foreign matter from flowing toward the downstream side of the trap 276. The trap 276 can have a configuration capable of being cooled by a cooler or by water cooling.

In addition, a bypass line 278 and an automatic pressure controller 280 may be installed on the exhaust line 272 at the upstream side of the collector 276. Valves V7 and V8 may be installed on the bypass line 278 and a portion of the exhaust line 272 extending parallel to the bypass line 278, respectively.

As in the deposition apparatuses (200A and 200C) shown in FIG. 3A and FIG. 3C , a heater 214 may be installed on the source material container 212. The source compound contained in the source material container 212 may be maintained at a relatively high temperature by the heater 214.

As in the deposition apparatus (200B and 200D) shown in FIG3B and FIG3D , a vaporizer 258 may be installed on the inflow line 266 of the thin film forming unit 250. The vaporizer 258 may vaporize the fluid supplied from the fluid delivery unit 210 in a liquid state, and may supply the vaporized source compound into the reaction chamber 254. The source compound vaporized by the vaporizer 258 may be supplied into the reaction chamber 254 together with the carrier gas supplied through the inflow line 268. The inflow of the source compound supplied into the reaction chamber 254 through the vaporizer 258 may be controlled by the valve V9.

In addition, as in the deposition apparatuses ( 200C and 200D) shown in FIGS. 3C and 3D , in order to generate plasma inside the reaction chamber 254 , the thin film forming unit 250 may include an RF power source 292 and an RF matching system 294 connected to the reaction chamber 254 .

In one embodiment, as shown in the figure, one source material container 212 may be connected to the reaction chamber 254. In one embodiment, as needed, the fluid delivery unit 210 may include a plurality of source material containers 212, and each of the plurality of source material containers 212 may be connected to the reaction chamber 254. The number of source material containers 212 connected to the reaction chamber 254 may vary.

In order to vaporize the source material for metal-containing film formation, which includes the organometallic adduct compound represented by the general formula (I), a vaporizer 258 may be used in one of the deposition apparatuses 200B and 200D shown in FIGS. 3B and 3D .

In order to form a metal-containing film on a substrate according to the method of manufacturing an integrated circuit device described with reference to FIG. 1 and FIG. 2 , one of the deposition apparatuses 200A, 200B, 200C, and 200D shown in FIG. 3A to FIG. 3D may be used. To this end, the organic metal addition compound having a structure of the general formula (I) according to the embodiment may be transported and supplied to a reaction space of a thin film forming apparatus (e.g., the reaction chamber 254 of the deposition apparatuses 200A, 200B, 200C, and 200D shown in FIG. 3A to FIG. 3D ) by various methods.

In one embodiment, in order to form a metal-containing film according to the method described with reference to FIGS. 1 and 2 , batch-type equipment rather than single-type equipment (e.g., deposition equipment 200A, 200B, 200C, and 200D shown in FIGS. 3A to 3D ) may be used to simultaneously form the metal-containing film on a plurality of substrates.

When a metal-containing film is formed according to the method of manufacturing an integrated circuit device according to an embodiment, the conditions for forming the metal-containing film may include a reaction temperature (substrate temperature), a reaction pressure, a deposition rate, or the like.

In one embodiment, the reaction temperature can be selected from a temperature range that allows the organometallic adduct compound (e.g., the organometallic adduct compound having the structure of general formula (I)) to react sufficiently, such as a temperature range of about 150° C. or higher, a temperature range of about 150° C. to about 600° C., or a temperature range of about 400° C. to about 550° C.

In the case of a thermal CVD process or an optical CVD process, the reaction pressure may be selected from a range of about 10 Pa to atmospheric pressure, or in the case of using plasma, the reaction pressure may be selected from a range of about 10 Pa to about 2000 Pa.

In addition, the deposition rate can be controlled by adjusting the conditions for supplying the source compound (e.g., vaporization temperature and vaporization pressure), the reaction temperature, and the reaction pressure. In the thin film formation method according to the embodiment, the deposition rate of the metal-containing film can be selected from a range of about 0.01 nm/min to about 100 nm/min (e.g., about 0.1 nm/min to about 50 nm/min). When the metal-containing film is formed by the ALD process, the number of ALD cycles can be adjusted to control the metal-containing film to a desired thickness.

In one embodiment, when a metal-containing film is formed by an ALD process, energy such as plasma, light, or voltage may be applied. The time point of applying energy may be selected differently. In one embodiment, energy such as plasma, light, or voltage may be applied at a time point when a source gas containing the organometallic addition compound is introduced into a reaction chamber, at a time point when the source gas is adsorbed onto a substrate, at a time point when an exhaust process is performed by blowing gas, at a time point when a reaction gas is introduced into a reaction chamber, or between each of these time points.

In one embodiment, after forming a metal-containing film using an organic metal adduct compound having a structure of general formula (I), the thin film forming method may further include performing an annealing process in an inert atmosphere, an oxidizing atmosphere, or a reducing atmosphere. In one embodiment, in order to fill the step formed at the surface of the metal-containing film, a reflow process may be performed on the metal-containing film as needed. Each of the annealing process and the reflow process may be performed at a temperature selected from a range of about 200° C. to about 1,000° C. (e.g., about 250° C. to about 500° C.).

In one embodiment, various metal-containing films may be formed by appropriately selecting the organometallic adduct compound, the other precursor used together with the organometallic adduct compound, the reaction gas, and the process conditions for thin film formation. In one embodiment, the metal-containing film formed according to the embodiment may include niobium atoms or tantalum atoms. In one embodiment, 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, or the like. The niobium alloy film may include, for example, a Nb-Hf alloy, a Nb-Ti alloy, or the like. The tantalum alloy film may include, for example, a Ta-Ti alloy, a Ta-W alloy, or the like. The metal-containing film can be used as a material for various components constituting an integrated circuit device. In one embodiment, the metal-containing film can be used for an electrode material of a dynamic random access memory (DRAM) device, a gate of a transistor, a resistor, a diamagnetic film for a hard device recording layer, a catalyst material for a solid polymer fuel cell, a conductive barrier film for a metal wiring line, a dielectric film for a capacitor, a barrier metal film for a liquid crystal, a component for a thin-film solar cell, a component for a semiconductor device, a nanostructure, or the like.

4A to 4J are cross-sectional views of stages in a method of manufacturing an integrated circuit device 300 (see FIG. 4J ) according to an embodiment.

4A , an interlayer insulating film 320 may be formed on a substrate 310 including a plurality of active regions AC, and then, a plurality of conductive regions 324 connected to at least one of the plurality of active regions AC via the interlayer insulating film 320 may be formed.

The substrate 310 may include a semiconductor (e.g., Si or Ge) or a compound semiconductor (e.g., SiGe, SiC, GaAs, InAs, or InP). The substrate 310 may include a conductive region, such as a doped well or a doped structure. The multiple active regions AC may be defined by multiple device isolation regions 312 formed in the substrate 310. The device isolation region 312 may include 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 multiple conductive regions 324 may be connected to one terminal of a switching device (e.g., a field effect transistor) formed on the substrate 310. The multiple conductive regions 324 may each include polycrystalline silicon, metal, conductive metal nitride, metal silicide, or a combination thereof.

4B , an insulating layer 328 may be formed to cover the interlayer insulating film 320 and the plurality of conductive regions 324. The insulating layer 328 may be used as an etch stop layer. The insulating layer 328 may include an insulating material having an etch selectivity relative to the interlayer insulating film 320 and a mold film 330 (see FIG. 4C ) formed in a subsequent process. The insulating layer 328 may include silicon nitride, silicon oxynitride, or a combination thereof.

4C , a mold film 330 may be formed on the insulating layer 328 .

The mold film 330 may include an oxide film. In one embodiment, the mold film 330 may include an oxide film, such as borophosphosilicate glass (BPSG), phosphosilicate glass (PSG), undoped silicate glass (USG), or a similar film. To form the mold film 330, a thermal CVD process or a plasma CVD process may be used. The mold film 330 may have a thickness of, for example, about 1,000 angstroms to about 20,000 angstroms. In one embodiment, the mold film 330 may include a support film. The support film may include a material having etching selectivity relative to the mold film 330. The support film may include a material having a relatively low etching rate in an etching atmosphere (e.g., in an etchant including ammonium fluoride (NH ₄ F), hydrofluoric acid (HF), and water) for removing the mold film 330 in a subsequent process. In one embodiment, the support film may include silicon nitride, silicon carbonitride, tantalum oxide, titanium oxide, or a combination thereof.

4D, a sacrificial film 342 and a mask pattern 344 may be sequentially formed on the mold film 330 in the stated order.

The sacrificial film 342 may include an oxide film. The mask pattern 344 may include an oxide film, a nitride film, a polysilicon film, a photoresist film, or a combination thereof. The region where the lower electrode of the capacitor is to be formed may be defined by the mask pattern 344.

4E , by dry etching the sacrificial film 342 and the mold film 330 using the mask pattern 344 as an etching mask and the insulating layer 328 as an etching stopper, a sacrificial pattern 342P and a mold pattern 330P may be formed to define a plurality of holes H1. Here, the insulating layer 328 may also be etched due to over-etching, and thus, an insulating pattern 328P exposing the plurality of conductive regions 324 may be formed.

4F, the mask pattern 344 may be removed from the resultant product shown in FIG. 4E, and then, a conductive film 350 for lower electrode formation may be formed to fill the plurality of holes H1 and cover the exposed surface of the sacrificial pattern 342P.

The conductive film 350 for forming the lower electrode may include a doped semiconductor, a conductive metal nitride, a metal, a metal silicide, a conductive oxide, or a combination thereof. In one embodiment, the conductive film 350 for forming the lower electrode may include, for example, NbN, TiN, TiAlN, TaN, TaAlN, W, WN, Ru, RuO ₂ , SrRuO ₃ , Ir, IrO ₂ , Pt, PtO, SRO (SrRuO ₃ ), BSRO ((Ba, Sr)RuO ₃ ), CRO (CaRuO ₃ ), LSCo ((La, Sr)CoO ₃ ) or a combination thereof. To form the conductive film 350 for forming the lower electrode, a CVD, metal organic CVD (MOCVD) or ALD process may be used.

In one embodiment, in order to form the conductive film 350 for lower electrode formation, a metal-containing film may be formed by the process P20 shown in FIG. 1 or by the method described with reference to FIG. 2 . In one embodiment, the conductive film 350 for lower electrode formation may include a niobium nitride (NbN) film. The NbN film may be a film formed by the process P20 shown in FIG. 1 or by the method described with reference to FIG. 2 . In order to form the conductive film 350 for lower electrode formation, one of the deposition apparatuses 200A, 200B, 200C, and 200D shown in FIGS. 3A to 3D may be used.

4G , a plurality of lower electrodes LE may be formed from the conductive film 350 for lower electrode formation by partially removing an upper portion of the conductive film 350 for lower electrode formation.

To form the plurality of lower electrodes LE, the upper portion of the conductive film 350 for lower electrode formation and the sacrificial pattern 342P (see FIG. 4F ) may be removed by an etchback process or a chemical mechanical polishing (CMP) process so that the upper surface of the mold pattern 330P is exposed.

4H, the outer surfaces of the plurality of lower electrodes LE may be exposed by removing the mold pattern 330P from the resultant shown in FIG4G. The mold pattern 330P may be removed by a lift-off process using an etchant including ammonium fluoride ( _NH4F ), hydrofluoric acid (HF), and water.

4I , a dielectric film 360 may be formed on the plurality of lower electrodes LE.

The dielectric film 360 may be formed to conformally cover the exposed surfaces of the plurality of lower electrodes LE.

In one embodiment, the dielectric film 360 may include, for example, uranium oxide, uranium oxynitride, uranium silicon oxide, zirconium oxide, zirconium silicon oxide, tantalum oxide, titanium oxide, barium strontium titanium oxide, barium titanium oxide, strontium titanium oxide, yttrium oxide, aluminum oxide, lead tantalum oxide, lead zinc niobate, or a combination thereof. The dielectric film 360 may be formed by an ALD process. The dielectric film 360 may have a thickness of, for example, about 50 angstroms or about 150 angstroms.

In one embodiment, before forming the dielectric film 360 on the plurality of lower electrodes LE as described with reference to FIG. 4I , the method for manufacturing the integrated circuit device 300 may further include a process for forming a lower interface film, the lower interface film covering the surface of each of the plurality of lower electrodes LE. In this case, the dielectric film 360 may be formed on the lower interface film. The lower interface film may include a metal-containing film including niobium or tantalum. In order to form the metal-containing film constituting the lower interface film, the process P20 shown in FIG. 1 or the method described with reference to FIG. 2 may be used. In order to form the lower interface film, one of the deposition equipment 200A, 200B, 200C and 200D shown in FIGS. 3A to 3D may be used.

4J , an upper electrode UE may be formed on the dielectric film 360. The lower electrode LE, the dielectric film 360, and the upper electrode UE may constitute a capacitor 370.

The upper electrode UE may include a doped semiconductor, a conductive metal nitride, a metal, a metal silicide, a conductive oxide, or a combination thereof. In one embodiment, the upper electrode UE may include, for example, NbN, TiN, TiAlN, TaN, TaAlN, W, WN, Ru, RuO ₂ , SrRuO ₃ , Ir, IrO ₂ , Pt, PtO, SRO (SrRuO ₃ ), BSRO ((Ba, Sr)RuO ₃ ), CRO (CaRuO ₃ ), LSCo ((La, Sr)CoO ₃ ) or a combination thereof. To form the upper electrode UE, a CVD, MOCVD, PVD, or ALD process may be used.

In one embodiment, to form the upper electrode UE, a metal-containing film may be formed by the process P20 shown in FIG. 1 or by the method described with reference to FIG. 2 . In one embodiment, the upper electrode UE may include a NbN film. The NbN film may be a film formed by the process P20 shown in FIG. 1 or by the method described with reference to FIG. 2 . To form the upper electrode UE, one of the deposition apparatuses 200A, 200B, 200C, and 200D shown in FIGS. 3A to 3D may be used.

In one embodiment, as shown in Figures 4A to 4J, each of the plurality of lower electrodes LE may have a pillar shape. In one embodiment, each of the plurality of lower electrodes LE may have a cross-sectional structure of a cup shape or a cylindrical shape with a closed bottom end.

In the integrated circuit device 300 manufactured by the method described with reference to FIGS. 4A to 4J , the capacitor 370 may include a lower electrode LE having a three-dimensional electrode structure. In order to help compensate for the reduction in capacitance due to the reduction in design rules, the aspect ratio of the lower electrode LE having a three-dimensional structure may be increased, and in order to form a lower electrode LE or an upper electrode UE with high quality in a deep and narrow three-dimensional space, an ALD process may be used. According to the method of manufacturing an integrated circuit device according to an embodiment described with reference to FIGS. 4A to 4J , the organic metal addition compound represented by the general formula (I) may be used to form the lower electrode LE or the upper electrode UE, thereby improving process stability.

The following examples and comparative examples are provided to highlight the characteristics of one or more embodiments, but it should be understood that the examples and comparative examples should not be interpreted as limiting the scope of the embodiments, and the comparative examples should not be interpreted as exceeding the scope of the embodiments. In addition, it should be understood that the embodiments are not limited to the specific details described in the examples and comparative examples.

Synthesis Example 1

Synthesis of the compound represented by Formula 2

Under an Ar atmosphere, 1.88 g (10.0 mmol) of NbF ₅ (V) and 20 ml of dehydrated dichloromethane were introduced into a 100 ml four-neck flask, and then stirred at ambient temperature. 0.97 g (10 mmol) of 3-fluoropyridine was added dropwise to the flask, and then the components were stirred at ambient temperature for 3 hours. The obtained product was subjected to solvent removal and purification, thereby obtaining 2.41 g of the compound represented by Formula 2. (Yield: 84.5%)

(analyze)

(1) 1H-nuclear magnetic resonance (1H-NMR) (heavy benzene)

8.27 ppm (1H, multiplet), 8.05 ppm (1H, multiplet), 6.21 ppm (1H, multiplet), 6.00 ppm (1H, multiplet)

(2) Element analysis (theoretical value)

Nb: 39.9% (32.6%), C: 21.4% (21.1%), H: 1.6% (1.4%), N: 5.1% (4.9%), F: 40.7% (40.0%)

Synthesis Example 2

Synthesis of the compound represented by Formula 4

Under Ar atmosphere, 1.88 g (10.0 mmol) of NbF ₅ (V) and 20 ml of dehydrated dichloromethane were introduced into a 100 ml four-necked flask, and then stirred at ambient temperature. 1.15 g (10 mmol) of 2,6-difluoropyridine was added dropwise to the flask, and then the components were stirred at ambient temperature for 4 hours. The obtained product was subjected to solvent removal and purification, thereby obtaining 2.75 g of the compound represented by Formula 4. (Yield: 90.8%)

(analyze)

(1) 1H-NMR (heavy benzene)

6.41 ppm (2H, quintet), 5.66 ppm (2H, doublet)

(2) Element analysis (theoretical value)

Nb: 31.2% (30.7%), C: 20.1% (19.8%), H: 1.5% (1.0%), N: 4.9% (4.6%), F: 44.4% (43.9%)

Synthesis Example 3

Synthesis of the compound represented by Formula 8

Under Ar atmosphere, 2.70 g (10.0 mmol) of NbCl ₅ (V) and 30 ml of dehydrated dichloromethane were introduced into a 100 ml four-neck flask, and then stirred at ambient temperature. 0.97 g (10 mmol) of 3-fluoropyridine was added dropwise to the flask, and then the components were stirred at ambient temperature for 4 hours. The obtained product was subjected to solvent removal and purification, thereby obtaining 3.25 g of the compound represented by Formula 8. (Yield: 88.4%)

(analyze)

(1) 1H-NMR (heavy benzene)

8.85 ppm (1H, multiplet), 8.53 ppm (1H, multiplet), 6.10 ppm (1H, multiplet), 5.91 ppm (1H, multiplet)

(2) Element analysis (theoretical value)

Nb: 26.1% (25.3%), C: 48.6% (48.3%), H: 1.6% (1.1%), N: 4.8% (3.8%), F: 5.5% (5.2%), Cl: 48.6% (48.3%)

Synthesis Example 4

Synthesis of the compound represented by Formula 14

Under an Ar atmosphere, 1.88 g (10.0 mmol) of NbF ₅ (V) and 20 ml of dehydrated dichloromethane were introduced into a 100 ml four-neck flask, and then stirred at ambient temperature. 1.14 g (10 mmol) of 3-chloropyridine was added dropwise to the flask, and then the components were stirred at ambient temperature for 3 hours. The obtained product was subjected to solvent removal and purification, thereby obtaining 2.32 g of a compound represented by Formula 14. (Yield: 77.0%)

(analyze)

(1) 1H-NMR (heavy benzene)

8.48 ppm (1H, multiplet), 8.18 ppm (1H, multiplet), 6.56 ppm (1H, multiplet), 6.06 ppm (1H, multiplet)

(2) Element analysis (theoretical value)

Nb: 31.5% (30.8%), C: 20.1% (19.9%), H: 1.9% (1.3%), N: 5.4% (4.7%), F: 32.2% (31.5%), Cl: 12.3% (11.8%)

Synthesis Example 5

Synthesis of the compound represented by Formula 27

Under an Ar atmosphere, 1.88 g (10.0 mmol) of NbF ₅ (V) and 20 ml of dehydrated dichloromethane were introduced into a 100 ml four-neck flask, and then stirred at ambient temperature. 0.93 g (10 mmol) of 4-methylpyridine was added dropwise to the flask, and then the components were stirred at ambient temperature for 3 hours. The obtained product was subjected to solvent removal and purification, thereby obtaining 2.50 g of a compound represented by Formula 27. (Yield: 89.0%)

(analyze)

(1) 1H-NMR (heavy benzene)

8.24 ppm (2H, multiplet), 6.07 ppm (2H, multiplet), 1.39 ppm (3H, singlet)

(2) Element analysis (theoretical value)

Nb: 33.5% (33.1%), C: 26.0% (25.6%), H: 2.9% (2.5%), N: 5.8% (5.0%), F: 34.2% (33.8%)

Synthesis Example 6

Synthesis of the compound represented by Formula 38

Under an Ar atmosphere, 1.88 g (10.0 mmol) of NbF ₅ (V) and 20 ml of dehydrated dichloromethane were introduced into a 100 ml four-neck flask, and then stirred at ambient temperature. 1.07 g (10 mmol) of 3-ethylpyridine was added dropwise to the flask, and then the components were stirred at ambient temperature for 3 hours. The obtained product was subjected to solvent removal and purification, thereby obtaining 2.60 g of the compound represented by Formula 38. (Yield: 88.1%)

(analyze)

(1) 1H-NMR (heavy benzene)

8.42 ppm (1H, singlet), 8.31 ppm (1H, multiplet), 6.62 ppm (1H, multiplet), 6.33 ppm (1H, multiplet), 1.74 ppm (2H, quartet), 0.57 ppm (3H, triplet)

(2) Element analysis (theoretical value)

Nb: 31.8% (31.5%), C: 29.0% (28.5%), H: 3.6% (3.1%), N: 5.2% (4.8%), F: 33.0% (32.2%)

Synthesis Example 7

Synthesis of the compound represented by Formula 75

Under an Ar atmosphere, 1.88 g (10.0 mmol) of NbF ₅ (V) and 20 ml of dehydrated dichloromethane were introduced into a 100 ml four-neck flask, and then stirred at ambient temperature. 1.47 g (10 mmol) of 4-(trifluoromethyl)pyridine was added dropwise to the flask, and then the components were stirred at ambient temperature for 3 hours. The obtained product was subjected to solvent removal and purification, thereby obtaining 3.08 g of the compound represented by Formula 75. (Yield: 92.0%)

(analyze)

(1) 1H-NMR (heavy benzene)

8.12 ppm (2H, singlet, broad peak), 6.28 ppm (2H, multiplet)

(2) Element analysis (theoretical value)

Nb: 28.2% (27.7%), C: 22.0% (21.5%), H: 1.6% (1.2%), N: 4.8% (4.2%), F: 46.0% (45.4%)

Synthesis Example 8

Synthesis of the compound represented by Formula 80

Under an Ar atmosphere, 2.70 g (10.0 mmol) of NbCl ₅ (V) and 30 ml of dehydrated dichloromethane were introduced into a 100 ml four-necked flask, and then stirred at ambient temperature. 1.47 g (10 mmol) of 3-(trifluoromethyl)pyridine was added dropwise to the flask, and the components were subsequently stirred at ambient temperature for 4 hours. The obtained product was subjected to solvent removal and purification, thereby obtaining 3.30 g of a compound represented by Formula 80. (Yield: 79.0%)

(analyze)

(1) 1H-NMR (heavy benzene)

9.43 ppm (1H, singlet), 8.73 ppm (1H, doublet), 6.62 ppm (1H, doublet), 5.91 ppm (1H, multiplet)

(2) Element analysis (theoretical value)

Nb: 23.0% (22.3%), C: 17.6% (17.3%), H: 1.6% (1.0%), N: 3.8% (3.4%), F: 14.0% (13.7%), Cl: 43.0% (42.5%)

Synthesis Example 9

Synthesis of the compound represented by formula 81

Under an Ar atmosphere, 2.70 g (10.0 mmol) of NbCl ₅ (V) and 30 ml of dehydrated dichloromethane were introduced into a 100 ml four-neck flask, and then stirred at ambient temperature. 1.47 g (10 mmol) of 4-(trifluoromethyl)pyridine was added dropwise to the flask, and the components were subsequently stirred at ambient temperature for 4 hours. The obtained product was subjected to solvent removal and purification, thereby obtaining 3.09 g of the compound represented by Formula 81. (Yield: 74.0%)

(analyze)

(1) 1H-NMR (heavy benzene)

8.70 ppm (2H, double peak), 6.27 ppm (2H, double peak)

(2) Element analysis (theoretical value)

Nb: 22.7% (22.3%), C: 17.9% (17.3%), H: 1.3% (1.0%), N: 4.0% (3.4%), F: 14.1% (13.7%), Cl: 42.9% (42.5%)

Synthesis Example 10

Synthesis of the compound represented by formula 121

Under an Ar atmosphere, 1.88 g (10.0 mmol) of NbF ₅ (V) and 20 ml of dehydrated dichloromethane were introduced into a 100 ml four-necked flask, and then stirred at ambient temperature. 1.83 g (10 mmol) of 2,3-difluoropyridine was added dropwise to the flask, and the components were subsequently stirred at ambient temperature for 3 hours. The obtained product was subjected to solvent removal and purification, thereby obtaining 2.78 g of a compound represented by Formula 121. (Yield: 75.0%)

(analyze)

(1) 1H-NMR (heavy benzene)

8.27 ppm (singlet, 1H), 6.18 ppm (multiplet, 1H)

(2) Element analysis (theoretical value)

Nb: 25.5% (25.0%), C: 19.8% (19.4%), H: 0.9% (0.5%), N: 4.1% (3.8%), F: 51.0% (51.2%)

Synthesis Example 11

Synthesis of the compound represented by formula 122

Under an Ar atmosphere, 1.88 g (10.0 mmol) of NbF ₅ (V) and 20 ml of dehydrated dichloromethane were introduced into a 100 ml four-necked flask, and then stirred at ambient temperature. 1.65 g (10 mmol) of 2-fluoro-5-(trifluoromethyl)pyridine was added dropwise to the flask, and the components were subsequently stirred at ambient temperature for 3 hours. The obtained product was subjected to solvent removal and purification, thereby obtaining 2.73 g of a compound represented by Formula 122. (Yield: 77.4%)

(analyze)

(1) 1H-NMR (heavy benzene)

8.58 ppm (singlet, 1H), 6.55 ppm (multiplet, 1H), 5.49 ppm (doublet, 1H)

(2) Element analysis (theoretical value)

Nb: 26.8% (26.3%), C: 20.9% (20.4%), H: 1.2% (0.9%), N: 4.1% (4.0%), F: 49.0% (48.4%)

Synthesis Example 12

Synthesis of the compound represented by formula 134

Under an Ar atmosphere, 1.88 g (10.0 mmol) of NbF ₅ (V) and 20 ml of dehydrated dichloromethane were introduced into a 100 ml four-neck flask, and then stirred at ambient temperature. 1.61 g (10 mmol) of 3-(2,2,2-trifluoroethyl)pyridine was added dropwise to the flask, and the components were subsequently stirred at ambient temperature for 3 hours. The obtained product was subjected to solvent removal and purification, thereby obtaining 2.83 g of a compound represented by Formula 134. (Yield: 81.2%)

(analyze)

(1) 1H-NMR (heavy benzene)

8.39 ppm (singlet, 1H), 8.30 ppm (singlet, 1H), 6.62 ppm (multiplet, 1H), 6.20 ppm (singlet/broad, 1H), 2.17 ppm (quartet, 2H)

(2) Element analysis (theoretical value)

Nb: 27.0% (26.6%), C: 24.9% (24.1%), H: 2.0% (1.7%), N: 4.4% (4.0%), F: 44.0% (43.6%)

Synthesis Example 13

Synthesis of the compound represented by formula 325

Under an Ar atmosphere, 1.88 g (10.0 mmol) of NbF ₅ (V) and 20 ml of dehydrated dichloromethane were introduced into a 100 ml four-neck flask, and then stirred at ambient temperature. 1.15 g (10 mmol) of 2,3-difluoropyridine was added dropwise to the flask, and then the components were stirred at ambient temperature for 4 hours. The obtained product was subjected to solvent removal and purification, thereby obtaining 2.58 g of the compound represented by Formula 325. (Yield: 85.1%)

(analyze)

(1) 1H-NMR (heavy benzene)

7.68 ppm (doublet, 1H), 6.12 ppm (multiplet, 1H), 5.79 ppm (multiplet, 1H)

(2) Element analysis (theoretical value)

Nb: 31.3% (30.7%), C: 20.4% (19.8%), H: 1.2% (1.0%), N: 5.0% (4.6%), F: 44.2% (43.9%)

Synthesis Example 14

Synthesis of the compound represented by formula 329

Under an Ar atmosphere, 1.88 g (10.0 mmol) of NbF ₅ (V) and 20 ml of dehydrated dichloromethane were introduced into a 100 ml four-neck flask, and then stirred at ambient temperature. 1.33 g (10 mmol) of 2,3,5-trifluoropyridine was added dropwise to the flask, and the components were subsequently stirred at ambient temperature for 3 hours. The obtained product was subjected to solvent removal and purification, thereby obtaining 2.44 g of a compound represented by Formula 329. (Yield: 75.9%)

(analyze)

(1) 1H-NMR (heavy benzene)

7.63 ppm (singlet, 1H), 5.61 ppm (multiplet, 1H)

(2) Element analysis (theoretical value)

Nb: 29.3% (29.0%), C: 18.9% (18.7%), H: 0.8% (0.6%), N: 4.7% (4.4%), F: 47.8% (47.4%)

Evaluation Examples 1 to 14 and Comparison with Evaluation Example 1

Next, the compounds of Formula 2, Formula 4, Formula 8, Formula 14, Formula 27, Formula 38, Formula 75, Formula 80, Formula 81, Formula 121, Formula 122, Formula 134, Formula 325 and Formula 329 obtained in Synthesis Examples 1 to 14 and the comparative compound 1 shown below were evaluated in the following method at 25°C, their melting points and atmospheric thermogravimetry-differential thermal analysis (TG-DTA) mass 50% reduction temperature (T1), and the results are shown in Table 1. [Comparative Compound 1]

Evaluation of melting point

The state of each compound at 25° C. was observed by naked eyes. The melting point of each compound that was solid at 25° C. was measured using a melting point measurement apparatus. A compound having a relatively low melting point may be suitable as a source material for thin film formation due to the ease of its supply.

(2) Evaluation of atmospheric TG-DTA

The mass 50% reduction temperature (T1) of each of the compounds of Formula 2, Formula 4, Formula 8, Formula 14, Formula 27, Formula 38, Formula 75, Formula 80, Formula 81, Formula 121, Formula 122, Formula 134, Formula 325 and Formula 329 obtained in Synthesis Examples 1 to 14 and Comparative Compound 1 was measured by using TG-DTA under atmospheric pressure, at an Ar flow rate of 100 ml/min, a heating rate of 10°C/min and a temperature scanning range of 30°C to 600°C.

Compounds with relatively low atmospheric TG-DTA mass 50% reduction temperatures (T1) may have high vapor pressures and may be suitable as source materials for thin film formation. Table 1 Evaluation Examples Compound State at 25℃ Melting point T1 (℃) Evaluation Example 1 Formula 2 Solid 46 186 Evaluation Example 2 Formula 4 Solid 45 231 Evaluation Example 3 Formula 8 Solid 148 257 Evaluation Example 4 Formula 14 Solid 55 207 Evaluation Example 5 Formula 27 Solid 62 225 Evaluation Example 6 Formula 38 Solid 31 217 Evaluation Example 7 Formula 75 Solid 60 171 Evaluation Example 8 Formula 80 Solid 128 252 Evaluation Example 9 Formula 81 Solid 104 249 Evaluation Example 10 Formula 121 Solid 36 137 Evaluation Example 11 Formula 122 Solid 42 175 Evaluation Example 12 Formula 134 Liquid - 175 Evaluation Example 13 Formula 325 Solid 60 187 Evaluation Example 14 Formula 329 Solid 71 148 Comparative evaluation example 1 Comparison with compound 1 Solid 154 276

In Table 1, it can be seen that the melting point of Comparative Compound 1 is equal to or greater than 150° C., and the melting points of the compounds of Formula 2, Formula 4, Formula 8, Formula 14, Formula 27, Formula 38, Formula 75, Formula 80, Formula 81, Formula 121, Formula 122, Formula 134, Formula 325, and Formula 329 obtained in Synthesis Examples 1 to 14 are less than 150° C. Specifically, it can be seen that the compounds of Formula 2, Formula 4, Formula 14, Formula 27, Formula 38, Formula 75, Formula 121, Formula 122, Formula 134, Formula 325, and Formula 329 have relatively low melting points, for example, their melting points are less than 75° C. In addition, the atmospheric TG-DTA mass 50% reduction temperature (T1) of the comparative compound 1 is equal to or greater than 275° C., and the atmospheric TG-DTA mass 50% reduction temperature (T1) of the compounds of Formula 2, Formula 4, Formula 8, Formula 14, Formula 27, Formula 38, Formula 75, Formula 80, Formula 81, Formula 121, Formula 122, Formula 134, Formula 325, and Formula 329 obtained in Synthesis Examples 1 to 14 is less than 260° C. It can be seen that the compounds according to the examples have relatively high vapor pressures. It can be seen that among the compounds of the examples, the compounds of Formula 2, Formula 4, Formula 14, Formula 27, Formula 38, Formula 75, Formula 121, Formula 122, Formula 134, Formula 325 and Formula 329 have particularly high vapor pressures because their atmospheric TG-DTA mass 50% reduction temperatures (T1) are less than 235°C.

Evaluation Examples 15 to 28 and Comparative Evaluation Example 2 (Formation of Metal-Containing Film)

A niobium nitride film was formed on a silicon substrate by using each of the compounds of Formula 2, Formula 4, Formula 8, Formula 14, Formula 27, Formula 38, Formula 75, Formula 80, and Formula 81 obtained in Synthesis Examples 1 to 9 and Comparative Compound 1 as source materials and using the deposition apparatus shown in FIG3A. The ALD process conditions for forming the niobium nitride film are as follows.

(condition)

Reaction temperature (substrate temperature): 250°C

Reaction gas: Ammonia

(Process)

Under the above conditions, 150 cycles were performed by defining the following series of processes (1) to (4) as one cycle.

Process (1): A process in which a source material vaporized at a source material container heating temperature of 90° C. and an internal pressure of the source material container of 100 Pa is introduced into a chamber, and the source material is deposited at an internal chamber pressure of 100 Pa for 30 seconds.

Process (2): A process to remove unreacted source materials by Ar purge for 10 seconds.

Process (3): The reaction gas is supplied and the reaction is carried out for 30 seconds at a chamber pressure of 100 Pa.

Process (4): A process to remove unreacted source materials by Ar purge for 10 seconds.

The thickness of each of the thin films obtained by the above process was measured by X-ray reflectivity, the compound of each of the thin films was identified by X-ray diffraction, and the amount of carbon in each of the thin films was measured by X-ray photoelectron spectroscopy, and the results are shown in Table 2. Table 2 Evaluation Examples Compound Film thickness Thin film compounds Carbon content Evaluation Example 15 Formula 2 6.0nm Nb Not detected Evaluation Example 16 Formula 4 5.0nm Nb Not detected Evaluation Example 17 Formula 8 3.0 nanometers Nb Not detected Evaluation Example 18 Formula 14 4.7 nanometers Nb Not detected Evaluation Example 19 Formula 27 4.0 nanometers Nb Not detected Evaluation Example 20 Formula 38 5.7 nanometers Nb Not detected Evaluation Example 21 Formula 75 4.3 nanometers Nb Not detected Evaluation Example 22 Formula 80 3.3 nanometers Nb Not detected Evaluation Example 23 Formula 81 3.7 nanometers Nb Not detected Evaluation Example 24 Formula 121 5.4nm Nb Not detected Evaluation Example 25 Formula 122 5.2nm Nb Not detected Evaluation Example 26 Formula 134 5.6nm Nb Not detected Evaluation Example 27 Formula 325 4.9 nm Nb Not detected Evaluation Example 28 Formula 329 4.8nm Nb Not detected Comparative evaluation example 2 Comparison with compound 1 2.3 nanometers Nb 5 atomic%

In Table 2, the detection limit of the carbon amount is 0.1 atomic %. In the results shown in Table 2, among the thin films obtained by the ALD method, the thin film obtained from Comparative Compound 1 contains carbon in an amount of 5 atomic %. On the other hand, it can be seen that the thin films obtained from the compounds of Formula 2, Formula 4, Formula 8, Formula 14, Formula 27, Formula 38, Formula 75, Formula 80, Formula 81, Formula 121, Formula 122, Formula 134, Formula 325, and Formula 329 obtained in Synthesis Examples 1 to 14 contain carbon in an amount equal to or less than 0.1 atomic % which is the detection limit, and therefore have high quality. In addition, as a result of evaluating the thickness of the thin film obtained after performing 150 ALD process cycles, it can be seen that the thickness of the thin film obtained from Comparative Compound 1 was 2.3 nm or less, and the thickness of the thin film obtained from the compounds of Formula 2, Formula 4, Formula 8, Formula 14, Formula 27, Formula 38, Formula 75, Formula 80, Formula 81, Formula 121, Formula 122, Formula 134, Formula 325, and Formula 329 obtained in Synthesis Example 1 to Synthesis Example 14 was 3.0 nm or more. Therefore, the productivity of the thin film forming process (according to the examples) is excellent.

As can be seen from the above evaluation examples, the organometallic addition compound according to the embodiment may have a relatively low melting point and a relatively high vapor pressure, and when used as a source material for forming a thin film by an ALD process or a CVD process, may help improve the productivity of thin film formation.

By way of summary and review, a source compound for metal-containing film formation has been considered which can provide excellent filling property and excellent step coverage when forming a metal-containing film required for manufacturing an integrated circuit device, and has advantages in process stability and mass-productivity due to its ease of handling.

One or more embodiments may provide an organometallic addition compound comprising niobium or tantalum as a metal.

One or more embodiments may provide a compound that can be used as a source compound that provides excellent thermal stability, process stability, and mass productivity in forming metal-containing films required for fabricating integrated circuit devices.

One or more embodiments may provide a method of fabricating an integrated circuit device that provides desired electrical properties by forming a metal-containing film with excellent quality using a compound that provides excellent process stability and large-scale productivity.

Exemplary embodiments have been disclosed herein, and although specific terms are employed, such terms are used and should be interpreted in a generic and illustrative sense only and not for limiting purposes. In some cases, unless expressly stated otherwise, as would be apparent to one of ordinary skill in the art prior to the filing of this application, features, characteristics, and/or elements described in connection with a particular embodiment may be used alone or in combination with features, characteristics, and/or elements described in connection with other embodiments. Therefore, it should be understood by one of ordinary skill in the art that various changes in form and detail may be made without departing from the spirit and scope of the invention as described in the claims below.

200A, 200B, 200C, 200D: deposition equipment 210: fluid transfer unit 212: source material container 214: heater 222, 262, 264, 266, 268: inflow pipeline 224: outflow pipeline 226, 278: bypass pipeline 250: film forming unit 252: base 254: reaction chamber 256: nozzle 258: vaporizer 270: exhaust system 272: exhaust pipeline 274: vacuum pump 276: collector 280: automatic pressure controller 292: RF power supply 294: RF matching system 300: integrated circuit device 310, W: substrate 312: device isolation area 320: interlayer insulating film 324: conductive area 328: insulating layer 328P: insulating pattern 330: molding film 330P: molding pattern 342: sacrificial film 342P: sacrificial pattern 344: mask pattern 350: conductive film 360: dielectric film 370: capacitor AC: active area H1: hole LE: lower electrode M1, M2, M3, M4, M5: mass flow controller (MFC) P10, P20, P21, P22, P23, P24, P25, P26: process UE: Upper electrode V1, V2, V3, V4, V5, V6, V7, V8, V9: Valve

The features will be apparent to those skilled in the art by describing the exemplary embodiments in detail with reference to the accompanying drawings, in which: FIG. 1 is a flow chart of a method for manufacturing an integrated circuit device according to an embodiment. FIG. 2 is a flow chart of an exemplary method for forming a metal-containing film according to the method for manufacturing an integrated circuit device according to an embodiment. FIGS. 3A to 3D are schematic diagrams of exemplary configurations of deposition equipment that can be used in a process for forming a metal-containing film in a method for manufacturing an integrated circuit device according to an embodiment. FIGS. 4A to 4J are cross-sectional views of stages in a method for manufacturing an integrated circuit device according to an embodiment.

P10, P20: Process

Claims (13)

An organometallic addition compound represented by the general formula (I):

Wherein, in the general formula (I), R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C5 straight-chain alkyl group, a substituted or unsubstituted C3 to C5 branched-chain alkyl group, a substituted or unsubstituted C2 to C5 straight-chain alkenyl group or a substituted or unsubstituted C3 to C5 branched-chain alkenyl group, at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a fluorine atom, at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a hydrogen atom, X is a halogen atom, and M is a niobium atom. The organometallic addition compound as claimed in claim 1, wherein one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a fluorine atom, and the rest of R ¹ , R ² , R ³ , R ⁴ and R ⁵ are hydrogen atoms. The organometallic addition compound as described in claim 1, wherein at least one of R ¹ and R ² is a fluorine atom. The organic metal addition compound as described in claim 1, wherein: X is a fluorine atom. A method for manufacturing an integrated circuit device, the method comprising forming a metal-containing film on a substrate using an organometallic addition compound represented by the general formula (I):

Wherein, in the general formula (I), R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C5 straight chain alkyl group, a substituted or unsubstituted C3 to C5 branched chain alkyl group, a substituted or unsubstituted C2 to C5 straight chain alkenyl group or a substituted or unsubstituted C3 to C5 branched chain alkenyl group, X is a halogen atom, and M is a niobium atom or a tantalum atom. The method of claim 5, wherein, in the general formula (I), at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ includes a halogen atom. The method as described in claim 5, wherein, in the general formula (I), at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a fluorine atom, a C1 to C5 straight-chain alkyl group substituted with a fluorine atom, a C3 to C5 branched-chain alkyl group substituted with a fluorine atom, a C2 to C5 straight-chain alkenyl group substituted with a fluorine atom, or a C3 to C5 branched-chain alkenyl group substituted with a fluorine atom. The method as described in claim 5, wherein, in the general formula (I): one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a hydrogen atom, another one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a fluorine atom, and another one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a C1 to C5 straight-chain alkyl group substituted with a fluorine atom, a C3 to C5 branched-chain alkyl group substituted with a fluorine atom, a C2 to C5 straight-chain alkenyl group substituted with a fluorine atom, or a C3 to C5 branched-chain alkenyl group substituted with a fluorine atom. The method as claimed in claim 5, wherein, in the general formula (I), at least one of R ¹ and R ² is a fluorine atom. The method of claim 5, wherein, in the general formula (I): X is a fluorine atom or a chlorine atom, M is a niobium atom, and at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a fluorine atom. The method of claim 5, wherein forming the metal-containing film comprises: supplying the organic metal addition compound represented by the general formula (I) to the substrate; and supplying a reaction gas to the substrate. The method of claim 11, wherein the reaction gas comprises NH ₃ , N ₂ plasma, an organic amine compound, a hydrazine compound, or a combination thereof. The method as claimed in claim 5, wherein, in the general formula (I): M is a niobium atom, and forming the metal-containing film includes forming a niobium nitride (NbN) film.

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