CN115819449A - Organometallic adduct compounds and methods of using the same to fabricate integrated circuit devices - Google Patents

Abstract

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

Description

Organometallic adduct compounds and methods of using the same to fabricate integrated circuit devices

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is based on and claims priority from korean patent application No.10-2021-0123465, filed on the korean intellectual property office on 9/15/2021, the disclosure of which is incorporated herein by reference in its entirety.

Technical Field

Embodiments relate to organometallic adduct compounds and methods of fabricating integrated circuit devices by using the organometallic adduct compounds.

Background

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

Disclosure of Invention

The embodiments may be achieved by providing an organometallic adduct compound represented by general formula (I),

general formula (I)

Wherein, in the general formula (I), R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ Each independently is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C5 linear alkyl group, a substituted or unsubstituted C3 to C5 branched alkyl group, a substituted or unsubstituted C2 to C5 linear alkenyl group, or a substituted or unsubstituted C3 to C5 branched 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 of manufacturing an integrated circuit device, the method comprising forming a metal-containing film on a substrate by using an organometallic adduct compound represented by general formula (I),

general formula (I)

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

Drawings

Exemplary embodiments, features or characteristics will become apparent to those skilled in the art by describing in detail exemplary embodiments with reference to the attached drawings, in which:

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

FIG. 2 is a flow diagram of an exemplary method of forming a metal-containing film in accordance with a method of manufacturing an integrated circuit device according to an embodiment;

FIGS. 3A-3D are schematic diagrams of an example configuration of a deposition apparatus that may be used in a process for forming a metal-containing film in an integrated circuit device fabrication method according to an embodiment; and

fig. 4A-4J are cross-sectional views of stages in a method of manufacturing an integrated circuit device according to an embodiment.

Detailed Description

As used herein, the term "substrate" may refer to the substrate itself, or a stacked structure comprising the substrate and some layer or film or the like formed on the surface of the substrate. In addition, as used herein, the term "substrate surface" may refer to the exposed surface of the substrate itself, or the outer surface of a layer or film or the like formed on the substrate. As used herein, the abbreviation "Me" refers to methyl, the abbreviation "Et" refers to ethyl, the abbreviation "nPr" refers to n-propyl, and the abbreviation "tBu" refers to t-butyl (1, 1-dimethylethyl). As used herein, the term "room temperature" or "ambient temperature" refers to a temperature of about 20 ℃ to about 28 ℃, which may vary depending on the season. As used herein, the term "or" is not an exclusive word, e.g., "a or B" includes a, B, or a and B.

The organometallic adduct compound according to the embodiment may have a structure in which a pyridine derivative is combined with a coordination metal compound in the form of an adduct. The organometallic adduct compound according to the embodiment may be represented by 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 linear alkyl group, a substituted or unsubstituted C3 to C5 branched alkyl group, a substituted or unsubstituted C2 to C5 linear alkenyl group, or a substituted or unsubstituted C3 to C5 branched alkenyl group.

X may be, for example, a halogen atom.

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

In an embodiment, in formula (I), R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ Each independently may be, for example, a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a neopentyl group, a 3-pentyl group, an ethylene 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 nonafluorotert-butyl group.

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

In an embodiment, in formula (I), R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ At least one of which may comprise, for example, a halogen atom.

In an embodiment, in formula (I), R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ At least one of them may be, for example, a fluorine atom-substituted C1 to C5 linear alkyl group, a fluorine atom-substituted C3 to C5 branched alkyl group, a fluorine atom-substituted C2 to C5 linear alkenyl group, or a fluorine atom-substituted C3 to C5 branched alkenyl group.

In an embodiment, in formula (I), R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ One of them can be, for example, a hydrogen atom, R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ Can be, for example, a fluorine atom, and R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ Still another of (A) may be, for example, a fluorine atom-substituted C1 to C5 linear alkyl group, a fluorine atom-substitutedA C3 to C5 branched alkyl group, a fluorine atom-substituted C2 to C5 linear alkenyl group, or a fluorine atom-substituted C3 to C5 branched alkenyl group.

In an embodiment, in formula (I), R ¹ And R ² At least one of which may be, for example, a fluorine atom.

In embodiments, in formula (I), M may be, for example, a niobium atom, and R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ At least one of which may be, for example, a halogen atom.

In embodiments, in formula (I), X may be, for example, a fluorine atom or a chlorine atom, M may be, for example, a niobium atom, and R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ At least one of which may be, for example, a fluorine atom.

In embodiments, in formula (I), M may be, for example, a niobium atom, and R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ At least one of them may be, for example, a fluorine atom-substituted C1 to C5 linear alkyl group, a fluorine atom-substituted C3 to C5 branched alkyl group, a fluorine atom-substituted C2 to C5 linear alkenyl group, or a fluorine atom-substituted C3 to C5 branched alkenyl group.

In embodiments, in formula (I), M may be, for example, a tantalum atom, and R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ At least one of them may be, for example, a fluorine atom-substituted C1 to C5 linear alkyl group, a fluorine atom-substituted C3 to C5 branched alkyl group, a fluorine atom-substituted C2 to C5 linear alkenyl group, or a fluorine atom-substituted C3 to C5 branched alkenyl group.

In embodiments, in formula (I), X may be, for example, a fluorine atom or a chlorine atom, and R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ At least one of which may include, for example, fluorine atoms.

In embodiments, in formula (I), X may be, for example, a fluorine atom, and R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ At least one of which may be, for example, a fluorine atom-substituted C1 to C5 linear alkyl group, a fluorine atom-substituted C3 to C5 branchedAn alkyl group, a fluorine atom-substituted C2 to C5 linear alkenyl group, or a fluorine atom-substituted C3 to C5 branched alkenyl group.

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

In an embodiment, in order to form a high-quality thin film with excellent productivity, in the general formula (I), R is when M is a niobium atom ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ Two to four of (A) may each be, for example, a hydrogen atom, and R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ One to three of them may be each, for example, a halogen atom, a C1 to C5 alkyl group, a C2 to C5 alkenyl group, or a fluorine atom-substituted C1 to C5 alkyl group. In an embodiment, R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ Three to four of (A) may each be, for example, a hydrogen atom, and R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ One to two of them may be each, for example, a halogen atom, a C1 to C5 alkyl group, a C2 to C5 alkenyl group, or a fluorine atom-substituted C1 to C5 alkyl group. In an 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 fluorine atom-substituted C1 to C5 alkyl group. In an embodiment, R ² 、R ³ And R ⁴ May each be, for example, a hydrogen atom, and R ¹ And R ⁵ Can each be taken as an exampleSuch as a halogen atom, a C1 to C5 alkyl group, a C2 to C5 alkenyl group, or a fluorine atom-substituted C1 to C5 alkyl group.

The organometallic adduct compound according to the embodiment may have a structure in which a pyridine derivative is combined with a coordination metal compound in the form of an adduct, and may provide excellent thermal stability. Therefore, when the organometallic adduct compound according to the embodiment is used as a precursor of a metal in forming a metal-containing film by a Chemical Vapor Deposition (CVD) process or an Atomic Layer Deposition (ALD) process, the organometallic adduct compound according to the embodiment can be stably delivered without being decomposed by heat during the delivery thereof from a storage container to a reaction chamber. In addition, when the organometallic adduct compound according to an embodiment has been delivered to a deposition reaction chamber for forming a metal-containing film, the organometallic adduct 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 by using the organometallic adduct compound according to the embodiment, a phenomenon that an undesired foreign substance (e.g., carbon residue) remains in the metal-containing film to be formed can be suppressed, and the organometallic adduct compound can 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 an integrated circuit device can be improved.

Examples of the organometallic adduct compounds according to the embodiments may be represented by formulas 1 to 456 below.

Organometallic addition compounds according to embodiments may be synthesized using suitable reactions. In an embodiment, nbF may be used ₅ (V)、NbCl ₅ (V)、TaF ₅ (V), or TaCl ₅ (V) reacting with a pyridine compound having a structure corresponding to a final structure to be synthesized in a dichloromethane solvent, and then the resulting solution may be subjected to solvent removal by distillation and purification to obtain a niobium compound or tantalum compound represented by the general formula (I).

The organometallic adduct 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 diagram of a method of manufacturing an integrated circuit device according to an embodiment.

Referring to fig. 1, in process step P10, a substrate may be prepared.

The substrate may comprise, for example, silicon, ceramic, glass, metal nitride, or combinations thereof. The ceramic may include, for example, silicon nitride, titanium nitride, tantalum nitride, titanium oxide, niobium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, or combinations thereof. The metal and metal nitride may each include, for example, ti, ta, co, ru, zr, hf, la, or combinations thereof. The substrate surface may have a flat shape, a spherical shape, a fibrous shape, or a scaly shape. In embodiments, the substrate surface may have a three-dimensional structure, such as a trench structure or the like.

In an embodiment, the substrate may have a configuration as described below with reference to the substrate 310 of fig. 4A.

In process step P20 of FIG. 1, a metal-containing film may be formed on a substrate by using a source material for forming the metal-containing film, the source material including an organometallic adduct compound represented by general formula (I).

The source material used to form the metal-containing film may include an organometallic adduct compound according to an embodiment. In an embodiment, the source material for forming the metal-containing film may include at least one of the organometallic adduct compounds represented by formulas 1 to 324, for example.

The source material used to form the metal-containing film can vary depending on the thin film to be formed. In an embodiment, the metal-containing film to be formed may include a niobium-containing film or a tantalum-containing film. In forming the niobium-containing film, an organometallic adduct compound according to general formula (I) in which M is a niobium atom may be used as the source material for forming the metal-containing film. In forming the tantalum-containing film, an organometallic adduct compound according to general formula (I) wherein M is a tantalum atom may be used as the source material for forming the metal-containing film.

In an embodiment, when the metal-containing film to be formed includes only a niobium atom or a tantalum atom as a metal atom, the source material for forming the metal-containing film may not include other metal compounds and semimetal compounds other than the niobium compound or the tantalum compound represented by the general formula (I).

In an embodiment, the metal-containing film to be formed may further include other metals other than niobium or tantalum. In embodiments, when the metal-containing film to be formed is a film that includes other metals or semi-metals in addition to niobium or tantalum, the source material used to form the metal-containing film may include compounds (hereinafter referred to as "other precursors"): the compound includes a desired metal or semimetal in addition to the organometallic adduct compound according to the embodiment. In embodiments, the source material used to form the metal-containing film may further include an organic solvent or a nucleophile, in addition to the organometallic adduct compound according to embodiments.

To form the metal-containing film according to process step P20 of FIG. 1, either a CVD process or an ALD process may be employed. The source material for forming a metal-containing film including the organometallic adduct compound according to the embodiment may be suitably used in an electroless deposition process, such as a CVD process or an ALD process.

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

When the metal-containing film is formed according to process step P20 of fig. 1 using a vapor transport method, the organometallic adduct compound represented by general formula (I) itself can be used as the source material for forming the metal-containing film. In forming the metal-containing film according to process step P20 of fig. 1 using a liquid transport method, 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 may be used as the source material for forming the metal-containing film. The source material used to form the metal-containing film may also include other precursors, nucleophiles, and the like.

In embodiments, in order to form a metal-containing film according to the integrated circuit device manufacturing method according to an embodiment, a multi-component chemical deposition method may be used. In the multi-component chemical deposition method, a method of independently vaporizing and supplying each component of the source material for forming a metal-containing film (hereinafter, may be referred to as "single source method"), or a method of obtaining a mixed source material by mixing a plurality of components into a desired composition in advance (hereinafter, may be referred to as "mixed source method") may be employed. When the mixed source method is used, a mixture of the organometallic addition compound and the other precursor, or a mixed solution in which the mixture is dissolved in an organic solvent according to the embodiment may be used as the source material for forming the metal-containing film. The mixture or mixed solution may further include a nucleophile.

The organic solvent may include a suitable organic solvent. In embodiments, the organic solvent may include: for example, an acetate ester 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 methylcyclohexanone; hydrocarbons such as hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, toluene, or xylene; cyano-containing hydrocarbons such as 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, and the like. The organic solvents exemplified above may be used alone or as a mixed solvent of at least two thereof, and may be considered from the viewpoint of solubility of the solute, its use temperature and boiling point, its flash point, and the like.

When the source material for forming a metal-containing film including the organometallic adduct compound according to an embodiment includes an organic solvent, the organometallic adduct compound and other precursors may be present in the organic solvent in a total amount of about 0.01mol/L to about 2.0mol/L, for example about 0.05mol/L to about 1.0 mol/L. In an embodiment, when the source material for forming the metal-containing film does not include other metal compounds or semi-metal compounds other than the organometallic addition compound according to the embodiment, the above total amount is an amount of the organometallic addition compound, and when the source material for forming the metal-containing film includes other metal compounds or semi-metal compounds (e.g., other precursors) other than the organometallic addition compound according to the embodiment, the above total amount is a sum of the amount of the organometallic addition compound and an amount of the other precursor.

When a multi-component chemical deposition process is employed to form a metal-containing film in accordance with an integrated circuit device fabrication method, other precursors that can be used with the organometallic addition compounds according to embodiments can include other suitable precursors that are used as source materials for forming metal-containing films.

In embodiments, other precursors that may be used to form metal-containing films according to integrated circuit device fabrication methods may include organic coordination compounds, such as alcohol compounds, glycol compounds, beta-diketone compounds, cyclopentadiene compounds, organic amine compounds, silicon compounds, or metal compounds.

Other precursors may include elements such as lithium (Li), sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti), zirconium (Zr), hafnium (Hf), 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), aluminum (Al), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), ruthenium (Ru), or lutetium (Lu).

Examples of the alcohol compound having an organic ligand of other precursor may include: alkyl alcohols such as methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, isobutanol, tert-butanol, pentanol, isopentyl alcohol, and tert-amyl alcohol; ether alcohols such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2- (2-methoxyethoxy) ethanol, 2-methoxy-1-methylethanol, 2-methoxy-1, 1-dimethylethanol, 2-ethoxy-1, 1-dimethylethanol, 2-isopropoxy-1, 1-dimethylethanol, 2-butoxy-1, 1-dimethylethanol, 2- (2-methoxyethoxy) -1, 1-dimethylethanol, 2-propoxy-1, 1-diethylethanol, 2-sec-butoxy-1, 1-diethylethanol and 3-methoxy-1, 1-dimethylpropanol; and dialkylamino alcohols, such as dimethylaminoethanol, ethylmethylaminoethanol, diethylaminoethanol, dimethylamino-2-pentanol, ethylmethylamino-2-pentanol, dimethylamino-2-methyl-2-pentanol, ethylmethylamino-2-methyl-2-pentanol, diethylamino-2-methyl-2-pentanol.

Examples of the diol compound which can be used as the organic complex compound of the other precursor may include 1, 2-ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 2, 4-hexanediol, 2-dimethyl-1, 3-propanediol, 2-diethyl-1, 3-propanediol, 1, 3-butanediol, 2, 4-butanediol, 2-diethyl-1, 3-butanediol, 2-ethyl-2-butyl-1, 3-propanediol, 2, 4-pentanediol, 2-methyl-1, 3-propanediol, 2-methyl-2, 4-pentanediol, 2, 4-hexanediol and 2, 4-dimethyl-2, 4-pentanediol.

Examples of the β -diketone compound which can be used as the organic complex compound of the other 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-dimethylheptane-3, 5-dione, 2, 6-dimethylheptane-3, 5-dione, 2, 6-trimethylheptane-3, 5-dione, 2, 6-tetramethylheptane-3, 5-dione, octane-2, 4-dione, 2, 6-trimethyloctane-3, 5-dione, 2, 6-dimethyloctane-3, 5-dione, 2, 9-dimethylnonane-4, 6-dione, 2-methyl-6-ethyldecane-3, 5-dione, and 2, 2-dimethyl-6-ethyldecane-3, 5-dione; a fluoro-substituted alkyl beta-diketone, for example, 1,1, 1-trifluoropentane-2, 4-dione, 1,1, 1-trifluoro-5, 5-dimethylhexane-2, 4-dione, 1, 5-hexafluoropentane-2, 4-dione and 1, 3-diperfluorohexylpropane-1, 3-dione; and also ether-substituted beta-diketones, for example, 1,1, 5-tetramethyl-1-methoxyhexane-2, 4-dione, 2,2, 6-tetramethyl-1-methoxyheptane-3, 5-dione and 2,2, 6-tetramethyl-1- (2-methoxyethoxy) heptane-3, 5-dione.

Examples of the cyclopentadiene compound which can be used as the organic complex compound of the other 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 complex compound of the other 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 the other precursor may be manufactured using a suitable method. In an embodiment, when an alcohol compound is used as the organic ligand, the precursor may be prepared by reacting an inorganic salt of the above element or a hydrate thereof with an alkali metal alkoxide of the alcohol compound. Examples of the inorganic salt of the above element or a hydrate thereof may include a halide of a metal, acetic acid, and the like. Examples of the alkali metal alkoxide may include sodium alkoxide, lithium alkoxide, potassium alkoxide, and the like.

When a single source method is employed, compounds having thermal and/or oxidative decomposition behavior similar to the organometallic adduct compounds according to embodiments may be used as other precursors. When the source mixing method is employed, a compound having thermal and/or oxidative decomposition behavior similar to that of the organometallic adduct compound according to the embodiment and not deteriorating by a chemical reaction or the like at the time of mixing may be used as the other precursor.

In forming a metal-containing film according to an integrated circuit device fabrication method according to an embodiment, a source material for forming the metal-containing film may include a nucleophile. The nucleophile may impart stability to the niobium compound or tantalum compound and/or other precursors according to embodiments. Nucleophiles may include: for example, glycol ethers such as glyme, diglyme or triglyme, tetraglyme; 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' -tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,4, 7-pentamethyldiethylenetriamine, 1,4,7, 10-hexamethyltriethylenetetramine or triethoxytriethylenediamine; cyclic polyamines such as cyclam or cyclen; heterocyclic compounds such as pyridine, pyrrolidine, piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1, 4-dioxane, oxazole, thiazole or oxathiolane (oxathiolane); beta-ketoesters such as methyl acetoacetate, ethyl acetoacetate, or 2-methoxyethyl acetoacetate; or a beta-diketone such as acetylacetone, 2, 4-hexanedione, 2, 4-heptanedione, 3, 5-heptanedione, or di-tert-valerylmethane. The nucleophile may be present in an amount of about 0.1mol to about 10mol (e.g., about 1mol to about 4 mol) based on 1mol of the total precursor.

It may be desirable to suppress the amounts of metal element impurities, halogen impurities (e.g., chlorine impurities, etc.), and organic impurities as much as possible in the source material for forming the metal-containing film, which is used to form the metal-containing film in accordance with the integrated circuit device manufacturing method according to the embodiment. In embodiments, the metal element impurities can each be present in the source material used to form the metal-containing film in an amount of about 100ppb (e.g., by weight) or less. In embodiments, the metallic elemental impurities can each be present in the metallic elemental impurities in an amount of about 10ppb or less, and the metallic elemental impurities can be present in a total amount of about 1ppm or less, for example about 100ppb or less. In an embodiment, in forming a thin film used as a gate insulating film, a gate conductive film, or a barrier film of a large scale integrated circuit (LSI), the amounts of an alkali metal element and an alkaline earth metal element, which will affect the electrical characteristics of the resulting thin film, can be made as small as possible. In embodiments, the halogen impurities may be present in the source material used to form the metal-containing film in an amount of about 100ppm or less, such as about 10ppm or less or about 1ppm or less.

In the source material used to form the metal-containing film, the organic impurities may be present in a total amount of about 500ppm or less, such as about 50ppm or less, or about 10ppm or less.

When water is present in the source material for forming the metal-containing film, the water may cause generation of particles in the source material or may cause generation of particles during formation of the thin film. In embodiments, the precursor, organic solvent, and nucleophilic reagent may be pre-treated with water removal prior to use. In each of the precursor, the organic solvent, and the nucleophile, water may be present in an amount of about 10ppm or less, for example about 1ppm or less.

In forming a metal-containing film according to an integrated circuit manufacturing method, in order to reduce particle contamination in the metal-containing film to be formed, the amount of particles in a source material for forming the metal-containing film can be minimized. In an embodiment, when particle measurement is performed on a liquid phase by a light scattering type particle detector, the number of particles larger than 0.3 μm in 1mL of a source material liquid for forming a metal-containing film may be 100 or less, and the number of particles larger than 0.2 μm in the 1mL of the liquid may be 1000 or less, for example, 100 or less.

In process step P20 of fig. 1, in order to form a metal-containing film by using the source material for forming a metal-containing film, process step P20 may include: for example, a process of introducing a source material for forming a metal-containing film into a deposition reaction unit in which a substrate is located by vaporization of the source material, and then forming a precursor thin film on the substrate by depositing the source material for forming the metal-containing film onto 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 forming the metal-containing film into the deposition reaction unit by vaporization of the source material, the gas delivery method, the liquid delivery method, the single source method, or the mixed source method described above may be employed.

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

The oxidizing gas may include, for example, O ₂ 、O ₃ 、O ₂ Plasma, H ₂ O、NO ₂ 、NO、N ₂ O (nitrous oxide), CO ₂ 、H ₂ O ₂ 、HCOOH、CH ₃ COOH、(CH ₃ CO) ₂ O, alcohol, peroxide, sulfur oxide, or combinations thereof.

Nitrating gasThe body may comprise, for example, NH ₃ 、N ₂ Plasma, organic amine compounds such as monoalkylamines, dialkylamines, trialkylamines or alkylenediamines, hydrazine compounds, or combinations thereof.

In process step P20 of fig. 1, when the metal oxide film including niobium atoms or tantalum atoms is formed, an oxidizing gas may be used as the reaction gas. In process step P20 of fig. 1, when the metal nitride film including niobium atoms or tantalum atoms is formed, a nitrating gas may be used as a reaction gas.

In an embodiment, in order to form a metal-containing film including niobium atoms or tantalum atoms in the process step P20 of fig. 1, a thermal CVD process (in which a thin film is formed by reacting a source gas including an organometallic adduct compound according to an embodiment, or a source gas and a reaction gas only by heat), a plasma CVD process in which a reaction is performed using heat and plasma, an optical CVD process in which a reaction is performed using heat and light, an optical plasma CVD process in which a reaction is performed using heat, light, and plasma, or an ALD process may be employed.

In forming the metal-containing film according to the process step P20 of fig. 1, the reaction temperature (substrate temperature), the reaction pressure, the deposition rate, and the like may be appropriately selected according to the desired thickness and type of the metal-containing film. The reaction temperature may be in the range of room or ambient temperature to about 600 ℃, for example, about 400 ℃ to about 550 ℃, which is sufficient to react the source material for forming the metal-containing film.

When forming a metal-containing film according to process step P20 of fig. 1, when an ALD process is employed, the thickness of the metal-containing film may be adjusted by adjusting the number of cycles of the ALD process. When an ALD process is employed to form a metal-containing film on a substrate, the ALD process may include: for example, a source material introduction process of introducing a vapor formed by vaporizing a source material for forming a metal-containing film including an organometallic adduct compound according to an embodiment into a deposition reaction unit; a precursor film forming process of forming a precursor film on a surface of the substrate by using the vapor; an exhaust process of exhausting unreacted source gas remaining in a reaction space above the substrate; and a process of forming a metal-containing film on the surface of the substrate by chemically reacting the precursor thin film with the reaction gas.

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

Fig. 2 is a flow diagram of an exemplary method of forming a metal-containing film in accordance with a method of manufacturing an integrated circuit device according to an embodiment. A method of forming a metal-containing film by an ALD process according to process step P20 of fig. 1 is described with reference to fig. 2.

Referring to fig. 2, in process step P21, a source gas including an organometallic adduct compound having a structure of general formula (I) may be vaporized.

In an embodiment, the source gas may comprise the source materials described above for forming metal-containing films. The process of vaporizing the source gas may be performed at about 0 ℃ to about 200 ℃. When the source gas is vaporized, the pressure within the source material container or vaporization chamber may be about 1Pa to about 10,000pa.

In process step 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 step P21 onto the substrate. In embodiments, the reaction temperature may range from room temperature to about 600 ℃, e.g., from about 400 ℃ to about 550 ℃. The reaction pressure can be from about 1Pa to about 10,000pa, for example from about 10Pa to about 1,000pa.

By supplying the vaporized source gas onto the substrate, an adsorption layer including a chemisorption layer and a physisorption layer of the vaporized source gas can be formed on the substrate.

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

The purge gas may include, for example, an inert gas (e.g., ar, he, or Ne), N ₂ Qi, etc.

In an embodiment, the exhaust may be performed by depressurizing a reaction space where the substrate is located, instead of by a purge process. In embodiments, the pressure of the reaction space may be maintained at about 0.01Pa to about 300Pa, for example about 0.01Pa to about 100Pa, in terms of reduced pressure.

In an embodiment, the following operations may also be performed: heating the substrate on which the metal source adsorption layer including niobium atoms or tantalum atoms is formed, or heat-treating a reaction chamber accommodating the substrate. The heat treatment may be carried out at a temperature of from room temperature to about 600 deg.C, such as from about 400 deg.C to about 550 deg.C.

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

In an 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 O ₂ 、O ₃ 、O ₂ Plasma, H ₂ O、NO ₂ 、NO、N ₂ O (nitrous oxide), CO ₂ 、H ₂ O ₂ 、HCOOH、CH ₃ COOH、(CH ₃ CO) ₂ O, alcohol, peroxide, sulfur oxide, or combinations thereof

In an embodiment, a metal nitride film including niobium atoms or tantalum atoms may be formed on a substrate, and a reaction gas may be, for example, NH ₃ 、N ₂ Plasma, organic amine compounds such as monoalkylamines, dialkylamines, trialkylamines or alkylenediamines, hydrazine compounds, or combinations thereof.

During process step P24, the reaction space may be maintained at a temperature of from room temperature to about 600 ℃, for example, from about 400 ℃ to about 550 ℃, so that the metal source adsorption layer including niobium atoms or tantalum atoms may be sufficiently reacted with the reaction gas. During process step P24, the pressure in the reaction space can be from about 1Pa to about 10,000pa, for example from about 10Pa to about 1,000pa.

During process step P24, the reactant gas may be plasma treated. The Radio Frequency (RF) output in plasma processing may be about 0W to about 1,500w, for example about 50W to about 600W.

In the process step P25, unnecessary by-products on the substrate may be removed by supplying a purge gas onto the substrate.

The purge gas may include, for example, an inert gas (e.g., ar, he, or Ne), N ₂ Qi, etc.

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

The thin film deposition process has a series of process steps including process steps P21 through P25, which may be defined as a cycle that may be repeated multiple times until a metal-containing film having a desired thickness is formed. In an embodiment, the one cycle is performed, an exhaust process may be performed by using a purge gas similarly to the process step P23 or the process step P25, thereby exhausting unreacted gas from the reaction chamber, and then, a subsequent cycle may be performed.

In embodiments, 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, and the like may be controlled. If the deposition rate of the metal-containing film is too high, the characteristics of the resulting metal-containing film may be deteriorated, and if the deposition rate of the metal-containing film is too low, the productivity may be lowered. In embodiments, the deposition rate of the metal-containing film can be from about 0.01nm/min to about 100nm/min, such as from about 0.1nm/min to about 50nm/min.

Various suitable changes and adjustments may be made in the process of forming the metal-containing film.

In an embodiment, to form a metal-containing film on a substrate, an organometallic adduct compound having a structure of formula (I) and at least one of other precursors, reaction gases, carrier gases, and purge gases may be supplied to the substrate simultaneously or sequentially. More detailed configurations of other precursors, reaction gases, carrier gases, and purge gases that can be supplied to the substrate simultaneously with the organometallic adduct compound having the structure of formula (I) are described above.

In an embodiment, in the process of forming the metal-containing film described with reference to fig. 2, a reaction gas may be supplied onto the substrate between each of the process steps P21 to P25.

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

The deposition apparatuses 200A, 200B, 200C, and 200D illustrated in fig. 3A to 3D may each include a fluid transfer unit 210, a thin film forming unit 250 in which a thin film is formed on a substrate W by performing a deposition process using a process gas input from a source material container 212 in the fluid transfer unit 210, and an exhaust system 270; the exhaust system 270 serves to exhaust gases, or reaction byproducts, which may remain after being used for the reaction in the thin film forming unit 250.

The thin film forming unit 250 may include a reaction chamber 254, and the reaction chamber 254 includes a susceptor 252 supporting the substrate W. A showerhead 256 for supplying gas inputted from the fluid transfer unit 210 to the substrate W may be installed at an upper end portion within the reaction chamber 254.

The fluid transfer unit 210 may include an inflow line 222 for supplying a carrier gas from the outside of each deposition apparatus to the source material container 212, and an outflow line 224 for supplying 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 by 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 device.

The source compound input from the source material container 212 may be supplied into the reaction chamber 254 through an inflow line 266 of the membrane forming unit 250, the inflow line 266 being connected to the outflow line 224 of the fluid transfer unit 210. The source compound input from the source material container 212 may be input into the reaction chamber 254 together with the carrier gas supplied through the inflow line 268, as needed. A valve V4 and an MFC M3 may be installed on the inflow line 268 through which the carrier gas flows.

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

Spent process gases and spent reaction byproducts in the reaction chamber 254 may be exhausted outside of the respective 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 mounted on the exhaust line 272. The vacuum pump 274 may remove the process gases and waste reaction byproducts exhausted from the reaction chamber 254.

A trap 276 may be installed on the exhaust line 272 upstream of the vacuum pump 274. The trap 276 may trap reaction byproducts generated, for example, from process gases that are not completely reacted in the reaction chamber 254, thereby preventing the reaction byproducts from flowing into the vacuum pump 274 on the downstream side of the trap 276.

The trap 276 installed on the exhaust line 272 may trap foreign substances, such as reaction byproducts generated by a reaction between process gases, so that the foreign substances may not flow toward the downstream side of the trap 276. The trap 276 may have a configuration that can be cooled by a cooler or water cooling.

Furthermore, a bypass line 278 and an automatic pressure controller 280 may be installed on the exhaust line 272 upstream of the trap 276. Valves V7 and V8 may be installed on bypass line 278 and the portion of exhaust line 272 that extends parallel to bypass line 278, respectively.

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

As in the deposition apparatuses (200B and 200D) shown in fig. 3B and 3D, 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 in a liquid state from the fluid transfer unit 210, 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 a carrier gas supplied through an inflow line 268. The inflow of source compound supplied to the reaction chamber 254 through the vaporizer 258 may be controlled by a valve V9.

In addition, as in the deposition apparatuses (200C and 200D) shown in fig. 3C and 3D, in order to generate plasma within 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 embodiments, one source material container 212 may be connected to the reaction chamber 254, as shown. In an embodiment, the fluid transfer 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, as desired. The number of source material containers 212 connected to the reaction chamber 254 may vary.

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

In order to form a metal-containing film on a substrate according to the integrated circuit device manufacturing method that has been described with reference to fig. 1 and 2, one of the deposition apparatuses 200A, 200B, 200C, and 200D shown in fig. 3A to 3D may be employed. For this, the organometallic adduct compound according to the embodiment having the structure of the general formula (I) can be transported and supplied into the reaction space of the thin film forming apparatus, for example, the reaction chamber 254 of the deposition apparatuses 200A, 200B, 200C, and 200D shown in fig. 3A to 3D, by various methods.

In an embodiment, in order to form the metal-containing film according to the method described with reference to fig. 1 and 2, the metal-containing film may be simultaneously formed on a plurality of substrates by using a batch-type apparatus instead of a single-type apparatus such as the deposition apparatuses 200A, 200B, 200C, and 200D shown in fig. 3A to 3D.

In forming the metal-containing film according to the integrated circuit device manufacturing method according to the embodiment, conditions for forming the metal-containing film may include a reaction temperature (substrate temperature), a reaction pressure, a deposition rate, and the like.

In embodiments, the reaction temperature may be selected from a temperature range that allows for sufficient reaction of the organometallic adduct compound (e.g., an organometallic adduct compound having a structure of formula (I)), such as a temperature range of about 150 ℃ or greater, a temperature range of about 150 ℃ to about 600 ℃, or a temperature range of about 400 ℃ to about 550 ℃.

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

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

In embodiments, energy, such as plasma, light, or voltage, may be applied when forming a metal-containing film by an ALD process. The point in time at which the energy is applied can be chosen to be different. In embodiments, energy such as plasma, light, or voltage may be applied at a point of time when the source gas including the organometallic adduct compound is introduced into the reaction chamber, at a point of time when the source gas is adsorbed onto the substrate, at a point of time when the exhaust process is performed by the purge gas, at a point of time when the reaction gas is introduced into the reaction chamber, or between each of these points of time.

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

In embodiments, a wide variety of metal-containing films can be formed by appropriately selecting the organometallic adduct compound, other precursors used with the organometallic adduct compound, reaction gases, and process conditions for forming the thin film. In an embodiment, a metal-containing film formed according to an embodiment may include niobium atoms or tantalum atoms. In an 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 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, an Nb-Hf alloy, an 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. Metal-containing films can be used as materials for various components that make up integrated circuit devices. In embodiments, the metal-containing film may be used for electrode materials of Dynamic Random Access Memory (DRAM) devices, gates of transistors, resistors, diamagnetic films for hard device recording layers, catalyst materials for solid polymer fuel cells, conductive barrier films for metal wiring, capacitor dielectric films, barrier metal films for liquid crystals, members for thin-film solar cells, members for semiconductor devices, nanostructures, and the like.

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

Referring to fig. 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 may be formed to be connected to at least one of the plurality of active regions AC through the interlayer insulating film 320.

The substrate 310 may include a semiconductor such as Si or Ge, or a compound semiconductor such as SiGe, siC, gaAs, inAs, or InP. The substrate 310 may include conductive regions such as doped wells or doped structures. The plurality of active regions AC may be defined by a plurality of device isolation regions 312 formed in the substrate 310. 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 plurality of conductive regions 324 may be connected to one terminal of a switching device such as a field effect transistor formed on the substrate 310. The plurality of conductive regions 324 may each comprise polysilicon, metal, conductive metal nitride, metal silicide, or combinations thereof.

Referring to fig. 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 serve as an etch stop layer. The insulating layer 328 may include an insulating material having an etching selectivity with respect to the interlayer insulating film 320 and a mold film 330 (refer to fig. 4C) formed in a subsequent process. The insulating layer 328 may include silicon nitride, silicon oxynitride, or a combination thereof.

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

The mold film 330 may include an oxide film. In an embodiment, the mold film 330 may include an oxide film such as borophosphosilicate glass (BPSG), phosphosilicate glass (PSG), undoped Silicate Glass (USG), and the like. 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 an embodiment, the mold film 330 may include a support film. The support film may include a material having an etch selectivity with respect to the mold film 330. The support film may be included for use in subsequent processes (e.g., in processes including ammonium fluoride (NH) ₄ F) Hydrofluoric acid (HF), and water) removes materials having a relatively low etch rate in the etching atmosphere of the mold film 330. In an embodiment, the support film may include silicon nitride, silicon carbonitride, tantalum oxide, titanium oxide, or a combination thereof.

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

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. An area in which a lower electrode of the capacitor is to be formed may be defined by the mask pattern 344.

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

Referring to fig. 4F, the mask pattern 344 may be removed from the resultant product of fig. 4E, and then, a conductive film 350 for forming a lower electrode 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 a lower electrode may include a doped semiconductor, a conductive metal nitride, a metal silicide, a conductive oxide, or a combination thereof. In an embodiment, the conductive film 350 for forming a 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. For forming the conductive film 350 for forming the lower electrode, CVD, metal Organic CVD (MOCVD), or ALD process may be used.

In an embodiment, in order to form the conductive film 350 for forming a lower electrode, a metal-containing film may be formed by the process step P20 of fig. 1 or by the method described with reference to fig. 2. In an embodiment, the conductive film 350 for forming a lower electrode may include an NbN film. The NbN film may be a film formed by process step P20 of fig. 1 or by the method described with reference to fig. 2. In order to form the conductive film 350 for forming a lower electrode, one of the deposition apparatuses 200A, 200B, 200C, and 200D illustrated in fig. 3A to 3D may be used.

Referring to fig. 4G, by partially removing the upper portion of the lower electrode forming conductive film 350, a plurality of lower electrodes LE can be formed from the lower electrode forming conductive film 350.

In order to form the plurality of lower electrodes LE, the upper portion of the conductive film 350 for forming the lower electrode and the sacrificial pattern 342P (refer to fig. 4F) may be removed by an etch-back process or a Chemical Mechanical Polishing (CMP) process such that the upper surface of the mold pattern 330P is exposed.

Referring to fig. 4H, by removing the mold pattern 330P from the resultant product of fig. 4G, the outer surfaces of the plurality of lower electrodes LE may be exposed. May be used including ammonium fluoride (NH) ₄ F) An etchant of hydrofluoric acid (HF) and water removes the mold pattern 330P through a lift-off process (lift-off process).

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

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

In an embodiment, the dielectric film 360 may include, for example, hafnium oxide, hafnium oxynitride, hafnium silicon oxide, zirconium silicon oxide, tantalum oxide, titanium oxide, barium strontium titanium oxide, barium titanium oxide, strontium titanium oxide, yttrium oxide, aluminum oxide, lead scandium 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 an embodiment, before forming the dielectric film 360 on the plurality of lower electrodes LE, as described with reference to fig. 4I, the method of manufacturing the integrated circuit device 300 may further include a process of forming a lower interface film covering a 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 can include a metal-containing film comprising niobium or tantalum. To form the metal-containing film constituting the lower boundary film, the process step P20 of fig. 1, or the method described with reference to fig. 2, may be employed. To form the lower interface film, one of the deposition apparatuses 200A, 200B, 200C, and 200D shown in fig. 3A to 3D may be used.

Referring to fig. 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 silicide, a conductive oxide, or a combination thereof. In an 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 an embodiment, in order to form the upper electrode UE, the metal-containing film may be formed by the process step P20 of fig. 1 or by the method described with reference to fig. 2. In an embodiment, the upper electrode UE may include an NbN film. The NbN film may be a film formed by process step P20 of 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 fig. 3A to 3D may be used.

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

In the integrated circuit device 300 manufactured by the method described with reference to fig. 4A to 4J, the capacitor 370 may include the 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 rule, the aspect ratio of the lower electrode LE having a three-dimensional structure may be increased, and in order to form the lower electrode LE or the upper electrode UE having high quality in a deep and narrow three-dimensional space, the ALD process may be used. According to the integrated circuit device manufacturing method according to the embodiment, which has been described with reference to fig. 4A to 4J, the organometallic adduct 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 features of one or more embodiments, but it should be understood that the examples and comparative examples should not be construed as limiting the scope of the embodiments, nor should the comparative examples be construed as being outside the scope of the embodiments. Furthermore, it is understood that the embodiments are not limited to the specific details described in the examples and comparative examples.

Synthesis example 1

Synthesis of Compound represented by formula 2

Under Ar atmosphere, 1.88g (10.0 mmo)l) NbF ₅ (V) and 20mL of dehydrated dichloromethane were introduced into a 100mL 4-necked flask, which was then stirred at ambient temperature. 0.97g (10 mmol) of 3-fluoropyridine was added dropwise to the flask, and then the components were stirred at ambient temperature for 3 hours. The resultant product was desolvated and purified, thereby obtaining 2.41g of the compound represented by formula 2. (yield 84.5%)

(analysis)

(1) 1H-NMR (heavy benzene)

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

(2) Elemental 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 Compound represented by formula 4

Under Ar atmosphere, 1.88g (10.0 mmol) of NbF ₅ (V) and 20mL of dehydrated dichloromethane were introduced into a 100mL 4-necked flask, which was then stirred at ambient temperature. 1.15g (10 mmol) of 2, 6-difluoropyridine are added dropwise to the flask, and the components are subsequently stirred at ambient temperature for 4 hours. The resultant product was desolvated and purified to obtain 2.75g of a compound represented by formula 4. (yield 90.8%)

(analysis)

(1) 1H-NMR (heavy benzene)

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

(2) Elemental 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 Compound represented by formula 8

Under Ar, 2.70g (10.0 mmol) of NbCl5 (V) and 30mL of dehydrated dichloromethane were introduced into a 100mL 4-necked flask, which was then stirred at ambient temperature. 0.97g (10 mmol) of 3-fluoropyridine was added dropwise to the flask, followed by stirring these components at ambient temperature for 4 hours. The resultant product was desolvated and purified, thereby obtaining 3.25g of the compound represented by formula 8. (yield 88.4%)

(analysis)

(1) 1H-NMR (heavy benzene)

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

(2) Elemental 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 Compound represented by formula 14

Under Ar atmosphere, 1.88g (10.0 mmol) of NbF ₅ (V) and 20mL of dehydrated dichloromethane were introduced into a 100mL 4-necked flask, which was then stirred at ambient temperature. 1.14g (10 mmol) of 3-chloropyridine were added dropwise to the flask, followed by stirring the components at ambient temperature for 3 hours. The resultant product was desolvated and purified to obtain 2.32g of a compound represented by formula 14. (yield 77.0%)

(analysis)

(1) 1H-NMR (heavy benzene)

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

(2) Elemental 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 a Compound represented by formula 27

Under Ar atmosphere, 1.88g (10.0 mmol) of NbF ₅ (V) and 20mL of dehydrated dichloromethane were introduced into a 100mL 4-necked flask, which was then stirred at ambient temperature. 0.93g (10 mmol) of 4-methylpyridine was added dropwise to the flask, followed by stirring the components at ambient temperature for 3 hours. The resultant product was desolvated and purified, thereby obtaining 2.50g of a compound represented by formula 27. (yield 89.0%)

(analysis)

(1) 1H-NMR (heavy benzene)

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

(2) Elemental 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 a Compound represented by formula 38

Under Ar atmosphere, 1.88g (10.0 mmol) of NbF was added ₅ (V) and 20mL of dehydrated dichloromethane were introduced into a 100mL 4-necked flask, which was then stirred at ambient temperature. 1.07g (10 mmol) of 3-ethylpyridine were added dropwise to the flask, followed by stirring the components at ambient temperature for 3 hours. The resultant product was desolvated and purified to obtain 2.60g of a compound represented by formula 38. (yield 88.1%)

(analysis)

(1) 1H-NMR (heavy benzene)

8.42ppm (1H, singlet), 8.31ppm (1H, multiplet), 6.62ppm (1H, multiplet), 6.33ppm (1H, multiplet), 1,74ppm (2H, quartet), 0.57ppm (3H, triplet)

(2) Elemental 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 a Compound represented by formula 75

Under Ar atmosphere, 1.88g (10.0 mmol) of NbF ₅ (V) and 20mL of dehydrated dichloromethane were introduced into a 100mL 4-necked flask, which was then stirred at ambient temperature. 1.47g (10 mmol) of 4- (trifluoromethyl) pyridine are added dropwise to the flask, and the components are subsequently stirred at ambient temperature for 3 hours. The resultant product was desolvated and purified to obtain 3.08g of a compound represented by formula 75. (yield 92.0%)

(analysis)

(1) 1H-NMR (heavy benzene)

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

(2) Elemental 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 Compound represented by formula 80

Under Ar atmosphere, 2.70g (10.0 mmol) of NbCl ₅ (V) and 30mL of dehydrated dichloromethane were introduced into a 100mL 4-necked flask, which was then stirred at ambient temperature. 1.47g (10 mmol) of 3- (trifluoromethyl) pyridine are added dropwise to the flask, and the components are subsequently stirred at ambient temperature for 4 hours. The resultant product was desolvated and purified to obtain 3.30g of a compound represented by formula 80. (yield 79.0%)

(analysis)

(1) 1H-NMR (heavy benzene)

9.43ppm (1H, singlet), 8.73ppm (1H, doublet), 6.62ppm (1H, doublet), 5,91ppm (1H, multiplet)

(2) Elemental 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 Compound represented by formula 81

Under Ar atmosphere, 2.70g (10.0 mmol) of NbCl ₅ (V) and 30mL of dehydrated dichloromethane were introduced into a 100mL 4-necked flask, which was then stirred at ambient temperature. 1.47g (10 mmol) of 4- (trifluoromethyl) pyridine are added dropwise to the flask, and the components are subsequently stirred at ambient temperature for 4 hours. The resultant product was desolvated and purified, thereby obtaining 3.09g of a compound represented by formula 81. (yield 74.0%)

(analysis)

(1) 1H-NMR (heavy benzene)

8.70ppm (2H, doublet), 6.27ppm (2H, doublet)

(2) Elemental 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 Compound represented by formula 121

Under Ar atmosphere, 1.88g (10.0 mmol) of NbF ₅ (V) and 20mL of dehydrated dichloromethane were introduced into a 100mL 4-necked flask, which was then stirred at ambient temperature. 1.83g (10 mmol) of 2, 3-difluoropyridine are added dropwise to the flask, and the components are subsequently stirred at ambient temperature for 3 hours. The resultant product was desolvated and purified, thereby obtaining 2.78g of a compound represented by formula 121. (yield 75.0%)

(analysis)

(1) 1H-NMR (heavy benzene)

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

(2) Elemental 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 a Compound represented by formula 122

Under Ar atmosphere, 1.88g (10.0 mmol) of NbF was added ₅ (V) and 20mL of dehydrated dichloromethane were introduced into a 100mL 4-necked flask, which was then stirred at ambient temperature. 1.65g (10 mmol) of 2-fluoro-5- (trifluoromethyl) pyridine are added dropwise to the flask, and the components are subsequently stirred at ambient temperature for 3 hours. The resultant product was desolvated and purified, thereby obtaining 2.73g of a compound represented by formula 122. (yield 77.4%)

(analysis)

(1) 1H-NMR (heavy benzene)

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

(2) Elemental 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 a Compound represented by formula 134

Under Ar atmosphere, 1.88g (10.0 mmol) of NbF ₅ (V) and 20mL of dehydrated dichloromethane were introduced into a 100mL 4-necked flask, which was then stirred at ambient temperature. 1.61g (10 mmol) of 3- (2, 2-trifluoroethyl) pyridine were added dropwise to the flask, followed by stirring the components at ambient temperature for 3 hours. The resulting product is desolvated andpurification was performed to obtain 2.83g of a compound represented by formula 134. (yield 81.2%)

(analysis)

(1) 1H-NMR (heavy benzene)

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

(2) Elemental 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 a Compound represented by formula 325

Under Ar atmosphere, 1.88g (10.0 mmol) of NbF ₅ (V) and 20mL of dehydrated dichloromethane were introduced into a 100mL 4-necked flask, which was then stirred at ambient temperature. 1.15g (10 mmol) of 2, 3-difluoropyridine are added dropwise to the flask, and the components are subsequently stirred at ambient temperature for 4 hours. The resultant product was desolvated and purified, thereby obtaining 2.58g of a compound represented by formula 325. (yield 85.1%)

(analysis)

(1) 1H-NMR (heavy benzene)

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

(2) Elemental 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 Compound represented by formula 329

Under Ar atmosphere, 1.88g (10.0 mmol) of NbF ₅ (V) and 20mL of dehydrated dichloromethane were introduced into a 100mL 4-necked flask, which was then stirred at ambient temperature. 1.33g (10 mmol) of 2,3, 5-trifluoropyridine were added dropwise to the flask, followed by stirring the components at ambient temperature for 3 hours. The resultant product was desolvated and purified, thereby obtaining 2.44g of the compound represented by formula 329. (yield 75.9%)

(analysis)

(1) 1H-NMR (heavy benzene)

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

(2) Elemental 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 comparative evaluation example 1

Next, the following evaluations were made for the compounds of formulae 2,4, 8, 14, 27, 38, 75, 80, 81, 121, 122, 134, 325, 329 obtained in synthesis examples 1 to 14 and comparative compound 1 shown below: the state at 25 ℃, melting point, and temperature (T1) at which the mass was reduced by 50% by thermogravimetry-differential thermal analysis (TG-DTA) at atmospheric pressure were as follows, and the results are shown in table 1.

[ comparative Compound 1]

Melting Point evaluation

The state of each compound at 25 ℃ was observed by naked eyes. The melting point of each compound which was solid at 25 ℃ was measured by using a melting point measuring apparatus. The compound having a relatively low melting point may be suitable as a source material for forming a thin film because of its easy supply.

(2) Evaluation of TG-DTA at atmospheric pressure

The compounds of formulae 2,4, 8, 14, 27, 38, 75, 80, 81, 121, 122, 134, 325 and 329 obtained in Synthesis examples 1 to 14 and comparative compound 1 were each tested for a 50% mass reduction at a temperature (T1) under atmospheric pressure by using TG-DTA under the conditions: the flow rate of Ar is 100mL/min, the heating rate is 10 ℃/min, and the temperature scanning range is 30 ℃ to 600 ℃.

A compound having a relatively low temperature (T1) at which the normal pressure TG-DTA mass decreases by 50% may have a high vapor pressure and may be suitable as a source material for forming a thin film.

TABLE 1

In table 1, it can be seen that the melting point of comparative compound 1 is 150 ℃ or more, and the melting points of the compounds of formulae 2,4, 8, 14, 27, 38, 75, 80, 81, 121, 122, 134, 325 and 329 obtained in synthesis examples 1 to 14 are less than 150 ℃. In particular, it can be seen that the compounds of formulae 2,4, 14, 27, 38, 75, 121, 122, 134, 325 and 329 have relatively low melting points, for example, melting points below 75 ℃. Further, the temperature (T1) at which the ordinary pressure TG-DTA mass of comparative compound 1 is reduced by 50% is equal to or more than 275 ℃ and the temperature (T1) at which the ordinary pressure TG-DTA mass of the compounds of formulae 2,4, 8, 14, 27, 38, 75, 80, 81, 121, 122, 134, 325 and 329 obtained in synthetic examples 1 to 14 is reduced by 50% is less than 260 ℃. It can be seen that the compounds according to the examples have a relatively high vapor pressure. It can be seen that among the compounds of the examples, the compounds of formulae 2,4, 14, 27, 38, 75, 121, 122, 134, 325 and 329 have particularly high vapor pressures because the temperature (T1) at which the normal pressure TG-DTA mass is reduced by 50% is less than 235 ℃.

Evaluation examples 15 to 28 and comparative evaluation example 2 (formation of Metal-containing film)

By using each of the compounds of formulae 2,4, 8, 14, 27, 38, 75, 80 and 81 obtained in synthesis examples 1 to 9 and comparative compound 1 as a source material, and using the deposition apparatus of fig. 3A, a niobium nitride film was formed on a silicon substrate. The ALD process conditions for forming the niobium nitride film are as follows.

(Condition)

Reaction temperature (substrate temperature): 250 ℃ C

Reaction gas: ammonia gas

(Process)

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

The process step (1): a step of introducing a source material vaporized under the conditions of a source material container heating temperature of 90 ℃ and a source material container internal pressure of 100Pa into the chamber and depositing the source material at an internal cavity pressure of 100Pa for 30 seconds.

A process step (2): a step of removing unreacted source material by Ar purge for 10 seconds.

A process step (3): and supplying a reaction gas and reacting at a chamber pressure of 100Pa for 30 seconds.

A process step (4): a step of removing unreacted source material by Ar purge for 10 seconds.

The thickness of each thin film obtained by the above-described process was measured by X-ray reflectance, the compound of each thin film was identified by X-ray diffraction, and the amount of carbon therein was measured by X-ray photoelectron spectroscopy, and the results are shown in table 2.

TABLE 2

Evaluation examples	Compound (I)	Film thickness	Thin film compounds	Amount of carbon
					Evaluation example 15	Formula 2	6.0nm	NbN	Not detected out
Evaluation example 16	Formula 4	5.0nm	NbN	Not detected out
					Evaluation example 17	Formula 8	3.0nm	NbN	Not detected out
Evaluation example 18	Formula 14	4.7nm	NbN	Not detected out
					Evaluation example 19	Formula 27	4.0nm	NbN	Not detected out
Evaluation example 20	Formula 38	5.7nm	NbN	Not detected out
					Evaluation example 21	Formula 75	4.3nm	NbN	Not detected out
Evaluation example 22	Formula 80	3.3nm	NbN	Not detected out
					Evaluation example 23	Formula 81	3.7nm	NbN	Not detected out
Evaluation example 24	Formula 121	5.4nm	NbN	Not detected out
					Evaluation example 25	Formula 122	5.2nm	NbN	Not detected out
Evaluation example 26	Formula 134	5.6nm	NbN	Not detected out
					Evaluation example 27	Formula 325	4.9nm	NbN	Undetected
Evaluation example 28	Formula 329	4.8nm	NbN	Not detected out
					Comparative evaluation example 2	Comparative Compound 1	2.3nm	NbN	5 atom%

In table 2, the detection limit of the amount of carbon is 0.1 atomic%. In the results of table 2, the thin film obtained from comparative compound 1 contained 5 atomic% of carbon in the thin film obtained by the ALD method. On the other hand, it can be seen that the thin films prepared from the compounds of formulae 2,4, 8, 14, 27, 38, 75, 80, 81, 121, 122, 134, 325 and 329 obtained in synthetic examples 1 to 14 contain carbon in an amount of 0.1 atomic% or less of the detection limit and thus have high quality. Further, as a result of evaluating the thickness of the thin film obtained after 150 cycles of the ALD process, it can be seen that the thickness of the thin film obtained from comparative compound 1 was 2.3nm or less, whereas the thickness of the thin film prepared from the compounds of formulae 2,4, 8, 14, 27, 38, 75, 80, 81, 121, 122, 134, 325 and 329 obtained in synthesis examples 1 to 14 was 3.0nm or more. Therefore, the thin film forming process (according to the embodiment) has excellent productivity.

As can be seen from the above evaluation examples, the organometallic adduct compounds according to the embodiments can 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 ALD or CVD process, can contribute to an increase in productivity of forming the thin film.

In view of the foregoing, source compounds for forming metal-containing films have been considered which are capable of providing excellent filling properties and excellent step coverage when forming metal-containing films required for integrated circuit device production, and which are advantageous in terms of process stability and mass productivity due to their ease of handling.

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

One or more embodiments may provide a compound capable of being used as a source compound, which may provide excellent thermal stability, process stability, and mass productivity in forming a metal-containing film required for integrated circuit device production.

One or more embodiments may provide a method of manufacturing an integrated circuit device that may provide desired electrical properties by forming a metal-containing film of excellent quality using a compound capable of providing excellent process stability and mass productivity.

Example embodiments are disclosed herein and, although specific terms are employed, they are used and are to be interpreted in a generic and descriptive sense only and not for purposes of limitation. In some instances, features, and/or elements described in connection with a particular embodiment may be used alone, or in combination with features, and/or element features described in connection with other embodiments, as will be apparent to those of ordinary skill in the art upon submission of the present application, unless otherwise specifically stated. It will, therefore, be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as set forth in the appended claims.

Claims (20)

1. An organometallic adduct compound represented by general formula (I):

general formula (I)

Wherein, in the general formula (I),

R ¹ 、R ² 、R ³ 、R ⁴ and R ⁵ Each independently is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C5 linear alkyl group, a substituted or unsubstituted C3To a C5 branched alkyl group, a substituted or unsubstituted C2 to C5 linear alkenyl group, or a substituted or unsubstituted C3 to C5 branched alkenyl group,

x is a halogen atom, and

m is a niobium atom or a tantalum atom.

2. The organometallic adduct compound of claim 1, wherein R is ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ At least one of which comprises a halogen atom.

3. The organometallic addition compound of claim 1 wherein R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ At least one of which is a fluorine atom, a fluorine atom-substituted C1 to C5 linear alkyl group, a fluorine atom-substituted C3 to C5 branched alkyl group, a fluorine atom-substituted C2 to C5 linear alkenyl group, or a fluorine atom-substituted C3 to C5 branched alkenyl group.

4. The organometallic adduct compound of claim 1, wherein:

R ¹ 、R ² 、R ³ 、R ⁴ and R ⁵ One of them is a hydrogen atom,

R ¹ 、R ² 、R ³ 、R ⁴ and R ⁵ Is a fluorine atom, and

R ¹ 、R ² 、R ³ 、R ⁴ and R ⁵ Still another of (a) is a fluorine atom-substituted C1 to C5 linear alkyl group, a fluorine atom-substituted C3 to C5 branched alkyl group, a fluorine atom-substituted C2 to C5 linear alkenyl group, or a fluorine atom-substituted C3 to C5 branched alkenyl group.

5. The organometallic adduct compound of claim 1, wherein R is ¹ And R ² At least one of which is a fluorine atom.

6. The organometallic adduct compound of claim 1, wherein:

m is a niobium atom, and

R ¹ 、R ² 、R ³ 、R ⁴ and R ⁵ At least one of which is a halogen atom.

7. The organometallic addition compound of claim 1, wherein:

x is a fluorine atom or a chlorine atom,

m is a niobium atom, and

R ¹ 、R ² 、R ³ 、R ⁴ and R ⁵ At least one of which is a fluorine atom.

8. The organometallic adduct compound of claim 1, wherein:

m is a niobium atom, and

R ¹ 、R ² 、R ³ 、R ⁴ and R ⁵ At least one of which is a fluorine atom, a fluorine atom-substituted C1 to C5 linear alkyl group, a fluorine atom-substituted C3 to C5 branched alkyl group, a fluorine atom-substituted C2 to C5 linear alkenyl group, or a fluorine atom-substituted C3 to C5 branched alkenyl group.

9. The organometallic adduct compound of claim 1, wherein:

m is a tantalum atom, and

R ¹ 、R ² 、R ³ 、R ⁴ and R ⁵ At least one of which is a fluorine atom, a fluorine atom-substituted C1 to C5 linear alkyl group, a fluorine atom-substituted C3 to C5 branched alkyl group, a fluorine atom-substituted C2 to C5 linear alkenyl group, or a fluorine atom-substituted C3 to C5 branched alkenyl group.

10. The organometallic addition compound of claim 1, wherein:

x is a fluorine atom or a chlorine atom, and

R ¹ 、R ² 、R ³ 、R ⁴ and R ⁵ At least one of which includes fluorine atoms.

11. The organometallic adduct compound of claim 1, wherein:

x is a fluorine atom, and

R ¹ 、R ² 、R ³ 、R ⁴ and R ⁵ At least one of which is a fluorine atom, a fluorine atom-substituted C1 to C5 linear alkyl group, a fluorine atom-substituted C3 to C5 branched alkyl group, a fluorine atom-substituted C2 to C5 linear alkenyl group, or a fluorine atom-substituted C3 to C5 branched alkenyl group.

12. A method of manufacturing an integrated circuit device, the method comprising forming a metal-containing film on a substrate by using an organometallic adduct compound represented by general formula (I),

general formula (I)

Wherein, in the general formula (I),

R ¹ 、R ² 、R ³ 、R ⁴ and R ⁵ Each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C5 linear alkyl group, a substituted or unsubstituted C3 to C5 branched alkyl group, a substituted or unsubstituted C2 to C5 linear alkenyl group, or a substituted or unsubstituted C3 to C5 branched alkenyl group,

x is a halogen atom, and

m is a niobium atom or a tantalum atom.

13. The process according to claim 12, wherein, in the general formula (I), R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ At least one of which comprises a halogen atom.

14. The process according to claim 12, wherein, in the general formula (I), R ¹ 、R ² 、R ³ 、R ⁴ And R ⁵ At least one of which is a fluorine atom, a fluorine atom-substituted C1 to CA C5 linear alkyl group, a fluorine atom-substituted C3 to C5 branched alkyl group, a fluorine atom-substituted C2 to C5 linear alkenyl group, or a fluorine atom-substituted C3 to C5 branched alkenyl group.

15. The method according to claim 12, wherein, in general formula (I):

R ¹ 、R ² 、R ³ 、R ⁴ and R ⁵ One of them is a hydrogen atom,

R ¹ 、R ² 、R ³ 、R ⁴ and R ⁵ Is a fluorine atom, and

R ¹ 、R ² 、R ³ 、R ⁴ and R ⁵ Still another of (a) is a fluorine atom-substituted C1 to C5 linear alkyl group, a fluorine atom-substituted C3 to C5 branched alkyl group, a fluorine atom-substituted C2 to C5 linear alkenyl group, or a fluorine atom-substituted C3 to C5 branched alkenyl group.

16. The process according to claim 12, wherein, in the general formula (I), R ¹ And R ² At least one of which is a fluorine atom.

17. The method according to claim 12, wherein, in general formula (I):

x is a fluorine atom or a chlorine atom,

m is a niobium atom, and

R ¹ 、R ² 、R ³ 、R ⁴ and R ⁵ At least one of them is a fluorine atom.

18. The method of claim 12, wherein forming the metal-containing film comprises:

supplying the organometallic addition compound represented by the general formula (I) onto the substrate; and

a reactive gas is supplied onto the substrate.

19. The method of claim 12, wherein the reactant gas comprises NH ₃ 、N ₂ Plasma, organic amine compounds, hydrazine compounds, or combinations thereof.

20. The method according to claim 12, wherein, in general formula (I):

m is a niobium atom, and

forming the metal-containing film includes forming a NbN film.

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