KR102665411B1 - Organometallic adduct compounds and method of manufacturing integrated circuit device using the same - Google Patents

Abstract

Disclosed is an organometallic addition compound of the following general formula (I) and a method of manufacturing an integrated circuit device using the same to form a metal-containing film on a substrate.
General formula (I)

In general formula (I), R ¹ , R ² , and R ³ are each independently a C1-C5 alkyl group, and at least one of R ¹ , R ² , and R ³ is at least one hydrogen atom contained in the alkyl group. It is substituted with a fluorine atom, M is a niobium atom, a tantalum atom, or a vanadium atom, X is a halogen atom, m is an integer from 3 to 5, and n is 1 or 2.

Description

Organic metal adduct compounds and method of manufacturing integrated circuit device using the same {Organometallic adduct compounds and method of manufacturing integrated circuit device using the same}

The technical idea of the present invention relates to an organometallic addition compound and a method of manufacturing an integrated circuit device using the same, and particularly to an organometallic addition compound containing niobium, tantalum, or vanadium as a metal and a method of manufacturing an integrated circuit device using the same. will be.

Due to the development of electronic technology, the down-scaling of semiconductor devices has recently progressed rapidly, and accordingly, the patterns that make up electronic devices are becoming finer. Accordingly, it can provide excellent embedding characteristics and excellent step coverage characteristics when forming a metal-containing film necessary for the manufacture of integrated circuit devices, and is easy to handle, which is advantageous in terms of process stability and mass production. Development of raw material compounds is necessary.

The technical problem to be achieved by the technical idea of the present invention is to provide an organometallic addition compound that can be used as a raw material compound that can provide excellent thermal stability, process stability, and mass productivity when forming a metal-containing film necessary for manufacturing integrated circuit devices. It is done.

Another technical problem to be achieved by the technical idea of the present invention is to provide an integrated circuit device that can provide desired electrical characteristics by forming a high-quality metal-containing film using a metal-containing raw material compound that can provide excellent process stability and mass production. The purpose is to provide a manufacturing method.

The organometallic addition compound according to one aspect according to the technical idea of the present invention is represented by the following general formula (I).

General formula (I)

In general formula (I),

R ¹ , R ² , and R ³ are each independently a C1-C5 alkyl group, and at least one of R ¹ , R ² , and R ³ has at least one hydrogen atom contained in the alkyl group replaced with a fluorine atom,

M is a niobium atom, a tantalum atom, or a vanadium atom,

X is a halogen atom,

m is an integer from 3 to 5,

n is 1 or 2.

A method of manufacturing an integrated circuit device according to an aspect according to the technical spirit of the present invention includes forming a metal-containing film on a substrate using an organometallic addition compound of general formula (I).

The organometallic addition compound according to the technical idea of the present invention exhibits sufficient volatility to be used in a deposition process, has a relatively low melting point and relatively high vapor pressure, is easy to handle and transport, and can form a high-quality metal-containing film with high productivity. In addition, the organic metal addition compound according to the technical idea of the present invention causes unwanted foreign substances such as carbon residue to remain in the metal-containing film to be formed using the CVD (chemical vapor deposition) process or the ALD (atomic layer deposition) process. This can be suppressed and can be suitably used as a raw material for forming a high-quality metal-containing film, and can improve the productivity of the manufacturing process of integrated circuit elements.

1 is a flowchart for explaining a method of manufacturing an integrated circuit device according to embodiments of the technical idea of the present invention.
FIG. 2 is a flow chart specifically explaining an exemplary method for forming a metal-containing film according to a method of manufacturing an integrated circuit device according to embodiments of the present invention.
3A to 3D are diagrams schematically showing the configuration of an exemplary deposition apparatus that can be used in the process of forming a metal-containing film in the manufacturing method of an integrated circuit device according to the technical spirit of the present invention.
Figures 4A to 4J are cross-sectional views shown according to the process sequence to explain a method of manufacturing an integrated circuit device according to embodiments of the technical idea of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The same reference numerals are used for the same components in the drawings, and duplicate descriptions thereof are omitted.

The term “substrate” used herein may refer to the substrate itself, or a laminated structure including the substrate and a predetermined layer or film formed on the surface. Additionally, in this specification, the term “surface of the substrate” may mean the exposed surface of the substrate itself, or the outer surface of a predetermined layer or film formed on the substrate. The term “room temperature” used in this specification is approximately 20 to 28°C and may vary depending on the season.

The organometallic addition compound according to the technical idea of the present invention has a structure in which an organic phosphate group is bonded to a coordination metal compound in the form of an adduct. The organometallic addition compound according to the technical idea of the present invention may be represented by the following general formula (I).

General formula (I)

In general formula (I), R ¹ , R ² , and R ³ are each independently a C1-C5 alkyl group, and at least one of R ¹ , R ² , and R ³ is at least one hydrogen atom contained in the alkyl group. It may be substituted with a fluorine atom. M is an element selected from the group 5 elements of the periodic table, such as a niobium atom, a tantalum atom, or a vanadium atom, .

In exemplary embodiments, at least one of R ¹ , R ² , and R ³ may be a straight-chain alkyl group. In other exemplary embodiments, at least one of R ¹ , R ² , and R ³ may be a branched alkyl group.

In exemplary embodiments, R ¹ , R ² , and R ³ are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, or 3-pentyl group.

In other exemplary embodiments, R ¹ , R ² , and R ³ may each independently be a trifluoromethyl group, a trifluoroethyl group, a hexafluoroisopropyl group, or a nonafluoro tert-butyl group.

In general formula (I), X may be an F atom, a Cl atom, a Br atom, or an I atom. When X is an F atom or a Cl atom, the melting point of the organometallic addition compound may be lowered and the vapor pressure of the organometallic addition compound may be higher.

Organometallic addition compounds according to embodiments of the technical spirit of the present invention may be liquid at room temperature. If the organometallic addition compound is liquid at room temperature, it can be easily handled. In General Formula (I), when at least one of R ¹ , R ² , and R ³ is a branched alkyl group, it may be advantageous for the organometallic addition compound to be in a liquid state at room temperature.

In exemplary embodiments, in general formula (I), M may be a niobium atom or a tantalum atom, and X may be a fluorine atom or a chlorine atom.

In example embodiments, in general formula (I), m may be 5 and n may be 1.

In exemplary embodiments, in general formula (I), M is a niobium atom or a tantalum atom, X is a chlorine atom, and R ¹ , R ² , and R ³ can each be a branched alkyl group.

In other exemplary embodiments, in general formula (I), M is a niobium atom or a tantalum atom, X is a fluorine atom, and R ¹ , R ² , and R ³ can each be a branched alkyl group.

In ^still other exemplary embodiments, in general formula (I), M ^is a ^niobium atom or a tantalum atom, It may be substituted with a fluorine atom.

In further exemplary embodiments, in general formula ( ^I ), M ^is a ^niobium atom or a tantalum atom, It may be substituted with a fluorine atom.

The organometallic addition compound according to the technical idea of the present invention has a structure in which an organic phosphate group is bonded to a coordination metal compound in the form of an adduct, and is performed through a chemical vapor deposition (CVD) process or an atomic layer deposition (ALD) process. When used as a metal precursor when forming a metal-containing film, the organic phosphate group plays a role in protecting the coordinated metal compound through coordination bonds when stored in a container, and when transferred to the deposition reaction chamber for forming a metal-containing film, the organic phosphate group within the reaction chamber It is easily decomposed by process temperature and may not affect the surface reaction for forming a metal-containing film.

Specific examples of organometallic addition compounds according to embodiments of the technical idea of the present invention may be represented by the following Formulas 1 to 16.

Methods for synthesizing organometallic addition compounds according to embodiments of the technical idea of the present invention are not particularly limited, and can be synthesized by applying known reactions. For example, pentachloride niobium and a phosphate ester having a structure corresponding to the final structure to be synthesized are reacted at about 25° C. in a dichloromethane solvent, and the solvent and unreacted products are distilled from the resulting solution. Afterwards, organometallic addition compounds according to embodiments of the technical idea of the present invention can be synthesized using a distillation and purification method.

Organometallic addition compounds according to embodiments of the technical idea of the present invention can be used as raw materials suitable for a CVD process or ALD process.

1 is a flowchart for explaining a method of manufacturing an integrated circuit device according to embodiments of the technical idea of the present invention.

Referring to Figure 1, a substrate is prepared in process P10.

The substrate may be made of silicon, ceramics, glass, metal, metal nitride, or a combination thereof. The ceramics may include silicon nitride, titanium nitride, tantalum nitride, titanium oxide, titanium nitride, niobium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, or a combination thereof. The metal and the metal nitride may each include Ti, Ta, Co, Ru, Zr, Hf, La, or a combination thereof, but are not limited thereto. The surface of the substrate may have a flat, spherical, fibrous, or scalelike shape. Alternatively, the surface of the substrate may have a three-dimensional structure such as a trench structure.

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

In step P20 of FIG. 1, a metal-containing film is formed on the substrate using a raw material for forming a metal-containing film containing an organometallic addition compound of general formula (I).

The raw material for forming the metal-containing film may include an organic metal addition compound according to the technical idea of the present invention. In exemplary embodiments, the raw material for forming the metal-containing film may include at least one organometallic addition compound represented by Formulas 1 to 16. In exemplary embodiments, the organometallic addition compound may be liquid at room temperature.

Raw materials for forming the metal-containing film may vary depending on the thin film to be formed. In example embodiments, the metal-containing film to be formed may be a niobium-containing film, a tantalum-containing film, or a vanadium-containing film. When forming the niobium-containing film, an organometallic addition compound of general formula (I) where M is a niobium atom can be used as a raw material for forming the metal-containing film. When forming the tantalum-containing film, an organometallic addition compound of general formula (I) where M is a tantalum atom can be used as a raw material for forming the metal-containing film. When forming the vanadium-containing film, an organometallic addition compound of general formula (I) where M is a vanadium atom can be used as a raw material for forming the metal-containing film. In this case, the raw material for forming the metal-containing film may contain only organometallic addition compounds according to the technical idea of the present invention and may not contain other metal compounds or semi-metallic compounds.

In other exemplary embodiments, the metal-containing film to be formed may further include another metal in addition to niobium, tantalum, or vanadium. For example, if the metal-containing film to be formed is a film that further contains a metal or semi-metal other than niobium, tantalum, or vanadium, the raw material for forming the metal-containing film may be in addition to the organometallic addition compound according to the technical idea of the present invention. It may contain a compound containing the desired metal or semimetal (hereinafter referred to as “other precursor”). In other exemplary embodiments, the raw material for forming the metal-containing film may further include an organic solvent or a nucleophilic reagent in addition to the organometallic addition compound according to the embodiments according to the technical idea of the present invention.

A CVD process or an ALD process can be used to form a metal-containing film according to process P20 of FIG. 1. The raw material for forming a metal-containing film containing an organic metal addition compound according to the technical idea of the present invention can be suitably used in a chemical vapor deposition process such as a CVD process or an ALD process.

When the raw material for forming a metal-containing film is used in a chemical vapor deposition process, the composition of the raw material for forming a metal-containing film can be appropriately selected depending on its transportation and supply method. The raw material transport method includes a gas transport method and a liquid transport method. In the gas transport method, the raw materials for forming a metal-containing film are stored in a container (hereinafter referred to as "raw material container") by heating or reducing pressure to vaporize the raw materials into a vapor state, and the vapor-state raw materials are stored as needed. It can be introduced into the chamber where the substrate is placed (hereinafter referred to as the "deposition reaction section") along with a carrier gas such as argon, nitrogen, helium, etc. used accordingly. In the liquid transport method, the raw material is transported in a liquid or solution state to a vaporization chamber, vaporized in the vaporization chamber by heating and/or reduced pressure to form vapor, and then the vapor can be introduced into the chamber.

When using the gas transport method to form a metal-containing film according to process P20 of FIG. 1, the organometallic addition compound of general formula (I) itself can be used as a raw material for forming the metal-containing film. When using the liquid transport method to form a metal-containing film according to step P20 in FIG. 1, the organometallic addition compound of general formula (I) itself, or the organometallic addition compound of general formula (I) is added to an organic solvent. The dissolved solution can be used as a raw material for forming a metal-containing film. The raw material for forming the metal-containing film may further include other precursors, nucleophilic reagents, etc.

In exemplary embodiments, a multi-component chemical vapor deposition method may be used to form a metal-containing film according to the manufacturing method of an integrated circuit device according to the technical spirit of the present invention. In the multi-component chemical vapor deposition method, the raw materials for forming a metal-containing film are supplied by vaporizing each component independently (hereinafter, may be referred to as a "single source method"), or the multi-component raw materials are supplied in advance. A method of vaporizing and supplying mixed raw materials mixed to a desired composition (hereinafter referred to as the “cocktail source method”) can be used. When using the cocktail sauce method, a mixture of an organic metal addition compound according to the technical idea of the present invention and another precursor, or a mixed solution obtained by dissolving the mixture in an organic solvent can be used as a raw material for forming a metal-containing film. The mixture or the mixed solution may further include a nucleophilic reagent.

The type of the organic solvent is not particularly limited, and organic solvents known in the art can be used. For example, the organic solvent includes acetic esters such as ethyl acetate, butyl acetate, and methoxyethyl acetate; tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dimethyl ether ethers such as butyl ether (dibutyl ether); Ketones such as dibutyl ketone, diethylbutyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, and cyclohexane; Hydrocarbons such as hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, toluene, xylene, etc.; 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1, 3-dicyanopropane (1,3-dicyanopropane), 1,4-dicyanobutane (1,4-dicyanobutane), 1,6-dicyanohexane (1,6-dicyanohexane), 1,4-dicyanocyclo Hydrocarbons with a cyano group such as hexane (1,4-dicyanocyclohexane), 1,4-dicyanobenzene, etc.; pyridine; Lutidine, etc. can be used. The organic solvents exemplified above can be used alone or as a mixed solvent of at least two types, taking into account the solubility of the solute, the relationship between the temperature of use, boiling point, and flash point.

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

When using the multi-component chemical vapor deposition method to form a metal-containing film according to the manufacturing method of an integrated circuit device according to the technical idea of the present invention, types of other precursors that can be used together with the organometallic addition compound according to the technical idea of the present invention is not particularly limited, and other known precursors that are used as raw materials for forming a metal-containing film can be used.

In exemplary embodiments, other precursors that can be used to form a metal-containing film according to the method of manufacturing an integrated circuit device according to the technical spirit of the present invention include, for example, an alcohol compound, a glycol compound, At least one organic coordination compound selected from a β-diketone compound, a cyclopentadiene compound, and an organic amine compound, silicon, and a metal It may be composed of a compound containing any one.

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

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

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

Examples of β-diketone compounds that can be used as organic coordination compounds of the other precursors include acetylacetone, hexane-2,4-dione, and 5-methylhexane-2,4. -Dione (5-methylhexane-2,4-dione), heptane-2,4-dione, 2-methylheptane-3,5-dione (2-methylheptane-3,5- dione), 5-methylheptane-2,4-dione (5-methylheptane-2,4-dione), 6-methylheptane-2,4-dione (6-methylheptane-2,4-dione), 2,2 -Dimethylheptane-3,5-dione (2,2-dimethylheptane-3,5-dione), 2,6-dimethylheptane-3,5-dione (2,6-dimethylheptane-3,5-dione), 2 ,2,6-trimethylheptane-3,5-dione (2,2,6-trimethylheptane-3,5-dione), 2,2,6,6-tetramethylheptane-3,5-dione (2,2 ,6,6-tetramethylheptane-3,5-dione), octane-2,4-dione (octane-2,4-dione), 2,2,6-trimethyloctane-3,5-dione (2,2, 6-trimethyloctane-3,5-dione), 2,6-dimethyloctane-3,5-dione (2,6-dimethyloctane-3,5-dione), 2,9-dimethylnonane-4,6-dione ( 2,9-dimethylnonane-4,6-dione), 2-methyl-6-ethyldecane-3,5-dione (2-methyl-6-ethyldecane-3,5-dione), 2,2-dimethyl-6 -alkyl-substituted β-diketones such as 2,2-dimethyl-6-ethyldecane-3,5-dione; 1,1,1-trifluoropentane-2,4-dione (1,1,1-trifluoropentane-2,4-dione), 1,1,1-trifluoro-5,5-dimethylhexane-2 ,4-dione (1,1,1-trifluoro-5,5-dimethylhexane-2,4-dione), 1,1,1,5,5,5-hexafluoropentane-2,4-dione (1 ,1,1,5,5,5-hexafluoropentane-2,4-dione), 1,3-diperfluorohexylpropane-1,3-dione (1,3-diperfluorohexylpropane-1,3-dione), etc. Fluorine substituted alkyl β-diketones; and 1,1,5,5-tetramethyl-1-methoxyhexane-2,4-dione (1,1,5,5-tetramethyl-1-methoxyhexane-2,4-dione), 2,2,6 ,6-Tetramethyl-1-methoxyheptane-3,5-dione (2,2,6,6-tetramethyl-1-methoxyheptane-3,5-dione), 2,2,6,6-tetramethyl- Ether substituted β-dione such as 1-(2-methoxyethoxy)heptane-3,5-dione (2,2,6,6-tetramethyl-1-(2-methoxyethoxy)heptane-3,5-dione) Ketones may be included, but are not limited thereto.

Examples of cyclopentadiene compounds that can be used as organic coordination compounds of the other precursors include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, and isocyclopentadiene. Isopropylcyclopentadiene, butylcyclopentadiene, sec-butylcyclopentadiene, isobutylcyclopentadiene, tert-butylcyclopentadiene, dimethyl Cyclopentadiene (dimethylcyclopentadiene), tetramethylcyclopentadiene, etc. may be mentioned, but it is not limited thereto.

Examples of organic amine compounds that can be used as organic coordination compounds of the other precursors include methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, Diethylamine, dipropylamine, diisopropylamine, ethylmethylamine, propylmethylamine, isopropylmethylamine, etc. are included, but are not limited thereto.

The other precursors may be known in the technical field to which the present invention pertains, and known methods may be used to prepare them. For example, when using an alcohol compound as an organic ligand, a precursor can be produced by reacting an inorganic salt of the above-described element or its hydrate with an alkali metal alkoxide of the alcohol compound. Here, examples of inorganic salts of the above-mentioned elements or their hydrates include metal halides, nitrates, and the like. Examples of the alkali metal alkoxide include sodium alkoxide, lithium alkoxide, and potassium alkoxide.

When using the single source method, a compound whose thermal and/or oxidative decomposition behavior is similar to the organometallic addition compound according to the technical idea of the present invention can be used as the other precursor. When using the cocktail sauce method, use a precursor that has thermal and/or oxidative decomposition behavior similar to that of the organometallic addition compound according to the technical idea of the present invention and does not cause deterioration due to chemical reaction, etc. when mixed. You can.

When forming a metal-containing film according to the manufacturing method of an integrated circuit device according to the technical idea of the present invention, the raw material for forming the metal-containing film may include a nucleophilic reagent. The nucleophilic reagent may impart stability to an organometallic addition compound and/or other precursor containing a niobium atom, a tantalum atom, or a vanadium atom, according to the technical spirit of the present invention. The nucleophilic reagent includes ethylene glycol ethers such as glyme, diglyme, triglyme, and tetraglyme; Crown ethers such as 18-crown-6, dicyclohexyl-18-crown-6,24-crown-8, dicyclohexyl-24-crown-8, and dibenzo-24-crown-8; Ethylenediamine, N,N'-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,1,4,7,7-pentamethyldiethylenetriamine, polyamines such as 1,1,4,7,10,10-hexamethyltriethylenetetramine and triethoxytriethyleneamine; Cyclic polyamines such as cyclam and cyclen; Pyridine, pyrrolidine, piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, oxazole , heterocyclic compounds such as thiazole and oxathiolane; β-ketone esters such as methyl acetoacetate, ethyl acetoacetate, and 2-methoxyethyl acetoacetate; Alternatively, β-diketones such as acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, and dipivaloyl methane may be mentioned. The nucleophilic reagent may be used in an amount of about 0.1 to about 10 mol, for example, about 1 mol to about 4 mol, based on 1 mol of the total amount of precursor.

According to the manufacturing method of an integrated circuit device according to the technical idea of the present invention, the amount of impurity metal elements, impurity halogens such as impurity chlorine, and impurity organic substances in the raw materials for forming the metal-containing film used to form the metal-containing film is reduced to the maximum. It needs to be suppressed. For example, in the raw materials for forming the metal-containing film, impurity metal elements may be contained at about 100 ppb or less for each element. For example, the raw material for forming the metal-containing film may contain about 10 ppb or less of impurity metal elements for each element, and the total amount of the impurity metal elements may be about 1 ppm or less, for example, about 100 ppb or less. there is. In particular, when forming a thin film used as a gate insulating film, gate conductive film, or barrier film of a large scale integrated circuit (LSI), the content of alkali metal elements and alkaline earth metal elements that affect the electrical properties of the resulting thin film must be kept as much as possible. You can do less. For example, the impurity halogen component in the raw material for forming the metal-containing film may be about 100 ppm or less, for example, about 10 ppm or less, or about 1 ppm or less.

Impurity organic components that may be included in the raw material for forming the metal-containing film may be included in a total amount of about 500 ppm or less, for example, about 50 ppm or less, and in particular, about 10 ppm or less.

If moisture is contained in the raw material for forming the metal-containing film, it may cause particles to be generated within the raw material or to generate particles during the formation of the thin film. Therefore, moisture can be removed from the precursor, organic solvent, and nucleophilic reagent before use. The water content of each of the precursor, organic solvent, and nucleophilic reagent may be about 10 ppm or less, for example, about 1 ppm or less.

When forming a metal-containing film according to a manufacturing method of an integrated circuit device, the particle content in the raw material for forming the metal-containing film can be minimized in order to reduce particle contamination in the metal-containing film to be formed. For example, when measuring particles by a light scattering type particle detector in the liquid phase, the number of particles larger than 0.3 μm in the raw material for forming the metal-containing film is 100 or less per 1 mL of the liquid phase. , the number of particles larger than 0.2 μm may be 1000 or less, for example, 100 or less per 1 mL of liquid.

In order to form a metal-containing film using the raw material for forming the metal-containing film in process P20 of FIG. 1, the raw material for forming the metal-containing film is vaporized and introduced into the deposition reaction unit where the substrate is located, and the metal-containing film is deposited on the surface of the substrate. A process of depositing raw materials for film formation to form a precursor thin film on the substrate, and reacting the precursor thin film with a reactive gas to form a metal-containing film containing niobium atoms, tantalum atoms, or vanadium atoms on the surface of the substrate. may include.

In order to vaporize the raw material for forming the metal-containing film and introduce it into the deposition reaction unit, the above-described gas transport method, liquid transport method, single source method, cocktail sauce method, etc. can be used.

The reactive gas is a gas that reacts with the precursor thin film. For example, the reactive gas may be an oxidizing gas, a reducing gas, or a nitriding gas.

The oxidizing gas is O ₂ , O ₃ , O ₂ plasma, H ₂ O, NO ₂ , NO, N ₂ O (nitrous oxide), CO, CO ₂ , H ₂ O ₂ , HCOOH, CH ₃ COOH, (CH ₃ CO) ₂ O, alcohol, peroxide, sulfur oxide, or a combination thereof.

The reducing gas may be H ₂ .

The nitriding gas is NH ₃ , N ₂ plasma, organic amine compounds such as monoalkylamine, dialkylamine, trialkylamine, alkylenediamine, hydrazine compound, Or it may be selected from a combination thereof.

When forming a metal oxide film containing niobium atoms, tantalum atoms, or vanadium atoms in step P20 of FIG. 1, the oxidizing gas can be used as the reactive gas. When forming a metal nitride film containing niobium atoms, tantalum atoms, or vanadium atoms in process P20 of FIG. 1, the nitriding gas can be used as the reactive gas.

In exemplary embodiments, in order to form a metal-containing film containing niobium atoms, tantalum atoms, or vanadium atoms in process P20 of FIG. 1, a raw material gas containing an organometallic addition compound according to the technical idea of the present invention, or A thermal CVD process in which a thin film is formed by reacting the raw material gas and the reactive gas with heat alone, a plasma CVD process using heat and plasma, an optical CVD process using heat and light, an optical plasma CVD process using heat, light and plasma, or an ALD process. Available.

When forming a metal-containing film according to process P20 of FIG. 1, the reaction temperature (substrate temperature), reaction pressure, deposition rate, etc. can be appropriately selected depending on the thickness and type of the desired metal-containing film. The reaction temperature may be selected within the range of room temperature to about 500°C, for example, about 150°C to about 400°C, which is a temperature at which the raw materials for forming the metal-containing film can sufficiently react.

When forming a metal-containing film according to process P20 of FIG. 1, when using an ALD process, the film thickness of the metal-containing film can be adjusted by adjusting the number of cycles of the ALD process. When forming a metal-containing film on the substrate using an ALD process, the vapor formed by vaporizing the raw material for forming a metal-containing film containing an organic metal addition compound according to the technical idea of the present invention is introduced into the deposition reaction unit. A gas introduction process, a precursor thin film forming process of forming a precursor thin film on the surface of the substrate using the vapor, an exhaust process of exhausting unreacted raw material gas remaining in a reaction space on the substrate, and a reactive precursor thin film. It may include a process of forming a metal-containing film on the surface of the substrate by chemically reacting with gas.

In exemplary embodiments, the process of vaporizing the raw material for forming the metal-containing film may be performed in a raw material container or in a vaporization chamber. The process of vaporizing the raw material for forming the metal-containing film may be performed at about 0°C to about 200°C. When vaporizing the raw material for forming the metal-containing film, the pressure inside the raw material container or vaporization chamber may be about 1 Pa to about 10,000 Pa.

FIG. 2 is a flow chart specifically explaining an exemplary method for forming a metal-containing film according to a method of manufacturing an integrated circuit device according to embodiments of the present invention. Referring to FIG. 2, a method of forming a metal-containing film using an ALD process according to process P20 of FIG. 1 will be described.

Referring to FIG. 2, in step P21, a source gas containing an organometallic addition compound having the structure of general formula (I) is vaporized.

In exemplary embodiments, the source gas may be made of the above-described raw material for forming a metal-containing film. The process of vaporizing the source gas may be performed at about 0°C to about 200°C. When vaporizing the source gas, the pressure inside the raw material container or vaporization chamber may be about 1 Pa to about 10,000 Pa.

In step P22, the source gas vaporized according to step P21 is supplied onto the substrate to form a metal source adsorption layer containing niobium atoms, tantalum atoms, or vanadium atoms on the substrate. At this time, the reaction temperature may be selected within the range of room temperature to about 500°C, for example, about 150°C to about 400°C. The reaction pressure may be from about 1 Pa to about 10,000 Pa, for example from about 10 Pa to about 1,000 Pa.

By supplying the vaporized source gas to the substrate, an adsorption layer including a chemisorbed layer and a physisorbed layer of the vaporized source gas may be formed on the substrate.

In process P23, a purge gas is supplied to the substrate to remove unnecessary by-products on the substrate.

As the purge gas, for example, an inert gas such as Ar, He, Ne, or N ₂ gas can be used.

In other exemplary embodiments, instead of the purge process, the reaction space in which the substrate is located may be depressurized and evacuated. At this time, for the pressure reduction, the pressure of the reaction space may be maintained at about 0.01 Pa to about 300 Pa, for example, about 0.01 Pa to about 100 Pa.

In exemplary embodiments, a process of heating the substrate on which the metal source adsorption layer containing niobium atoms, tantalum atoms, or vanadium 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 500°C, for example, from about 50°C to about 400°C.

In step P24, a reactive gas is supplied onto the metal source adsorption layer formed on the substrate to form a metal-containing film at the atomic layer level.

In exemplary embodiments, when forming a metal oxide film including niobium atoms, tantalum atoms, or vanadium atoms on the substrate, the reactive gas is O ₂ , O ₃ , O ₂ plasma, H ₂ O, NO ₂ , NO, N ₂ O (nitrous oxide), CO, CO ₂ , H ₂ O ₂ , HCOOH, CH ₃ COOH, (CH ₃ CO) ₂ O, alcohol, peroxide, sulfur oxide, or a combination thereof. It may be an oxidizing gas of choice.

In other exemplary embodiments, when forming a metal nitride film including niobium atoms, tantalum atoms, or vanadium atoms on the substrate, the reactive gas is NH ₃ , N ₂ plasma, monoalkyl amine, It may be selected from dialkylamine, trialkylamine, organic amine compound, hydrazine compound, or a combination thereof.

In still other exemplary embodiments, the reactive gas may be a reducing gas, such as H ₂ .

During process P24, the reaction space is maintained at a temperature ranging from room temperature to about 500° C., for example, about 50° C., so that the metal source adsorption layer containing the niobium atoms, tantalum atoms, or vanadium atoms and the reactive gas can sufficiently react. The temperature may be maintained from about 400°C to about 400°C or from about 50°C to about 200°C. While performing process P24, the pressure of the reaction space may be about 1 Pa to about 10,000 Pa, for example, about 10 Pa to about 1,000 Pa.

The reactive gas may be plasma treated while performing process P24. Radio frequency (RF) output during the plasma treatment may be about 0 W to about 1,500 W, for example, about 50 W to about 600 W.

In process P25, a purge gas is supplied to the substrate to remove unnecessary by-products on the substrate.

As the purge gas, for example, an inert gas such as Ar, He, Ne, or N ₂ gas can be used.

In step P26, steps P21 to P25 in FIG. 2 are repeated until a metal-containing film of the desired thickness is formed.

The thin film deposition process consisting of a series of processes consisting of steps P21 to P25 can be considered as one cycle, and the cycle can be repeated multiple times until a metal-containing film of a desired thickness is formed. In exemplary embodiments, after performing the above one cycle, an exhaust process using a purge gas is performed similar to process P23 or process P25 to exhaust unreacted gases from the reaction chamber, and then a subsequent cycle is performed. You can.

In exemplary embodiments, raw material supply conditions (eg, vaporization temperature or vaporization pressure of the raw material), reaction temperature, reaction pressure, etc. may be controlled to control the deposition rate of the metal-containing film. If the deposition rate of the metal-containing film is too high, the characteristics of the resulting metal-containing film may deteriorate, and if the deposition rate of the metal-containing film is too low, productivity may decrease. For example, the deposition rate of the metal-containing film may be about 0.01 nm/min to about 100 nm/min, for example, about 1 nm/min to about 50 nm/min.

The process of forming a metal-containing film described with reference to FIG. 2 is merely an example, and various modifications and changes are possible within the scope of the technical idea of the present invention.

For example, in order to form a metal-containing film on the substrate, an organometallic addition compound having the structure of general formula (I) is applied to the substrate together with at least one of another precursor, a reactive gas, a carrier gas, and a purge gas, or sequentially. It can be supplied to the table. More detailed configurations of other precursors, reactive gases, carrier gases, and purge gases that can be supplied on the substrate together with the organometallic addition compound having the structure of general formula (I) are as described above.

In other exemplary embodiments, in the metal-containing film formation process described with reference to FIG. 2, a reactive gas may be supplied on the substrate between each of processes P21 to P25.

3A to 3D each schematically show the configuration of exemplary deposition devices 200A, 200B, 200C, and 200D that can be used in the process of forming a metal-containing film in the manufacturing method of an integrated circuit device according to the technical spirit of the present invention. It is a drawing.

The deposition devices 200A, 200B, 200C, and 200D illustrated in FIGS. 3A to 3D each use a fluid delivery unit 210 and a process gas supplied from the raw material container 212 in the fluid delivery unit 210. It includes a thin film forming unit 250 in which a deposition process to form a thin film on the substrate W is performed, and an exhaust system 270 for discharging remaining gas or reaction by-products used in the reaction in the thin film forming unit 250. do.

The thin film forming unit 250 includes a reaction chamber 254 provided with a susceptor 252 supporting the substrate W. A shower head 256 is installed at the upper end of the reaction chamber 254 to supply gas supplied from the fluid delivery unit 210 onto the substrate W.

The fluid transmission unit 210 includes an inflow line 222 for supplying a carrier gas from the outside to the raw material container 212, and an outflow line for supplying the raw material compound contained in the raw material container 212 to the thin film forming unit 250. Includes (224). Valves (V1, V2) and mass flow controllers (MFC) (M1, M2) may be installed in the inlet line 222 and the outlet line 224, respectively. The inlet line 222 and the outlet line 224 may be interconnected through a bypass line 226. A valve (V3) is installed in the bypass line 226. Valve V3 may be pneumatically actuated by an electric motor or other remotely controllable means.

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

The thin film forming unit 250 includes an inlet line 262 for supplying a purge gas into the reaction chamber 254 and an inlet line 264 for supplying a reactive gas. Valves (V5, V6) and MFCs (M4, M5) may be installed in the inlet lines 262 and 264, respectively.

Process gases used in the reaction chamber 254 and reaction by-products for disposal may be discharged to the outside through the 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 in the exhaust line 272. The vacuum pump 274 may serve to remove process gases discharged from the reaction chamber 254 and reaction by-products for disposal.

A trap 276 may be installed upstream of the vacuum pump 274 in the exhaust line 272. For example, the trap 276 may capture reaction by-products generated by process gas that has not completely reacted within the reaction chamber 254 and prevent them from flowing into the vacuum pump 274 on the downstream side.

The trap 276 installed in the exhaust line 272 can capture deposits such as reaction by-products generated by reactions between process gases and prevent them from flowing downstream of the trap 276. Trap 276 may be configured to be cooled by a cooler or water cooling.

Additionally, a bypass line 278 and an automatic pressure controller 280 may be installed in the exhaust line 272 upstream of the trap 276. Valves V7 and V8 may be installed in the bypass line 278 and the exhaust line 272 in portions extending in parallel with the bypass line 278, respectively.

As in the deposition apparatuses 200A and 200C illustrated in FIGS. 3A and 3C, a heater 214 may be installed in the raw material container 212. The temperature of the raw material compound contained in the raw material container 212 can be maintained at a relatively high temperature by the heater 214.

As in the deposition devices 200B and 200D illustrated in FIGS. 3B and 3D, a vaporizer 258 may be installed in the inlet line 266 of the thin film forming unit 250. The vaporizer 258 vaporizes the fluid supplied in a liquid state from the fluid delivery unit 210 and supplies the vaporized raw compound into the reaction chamber 254. The raw compound vaporized in the vaporizer 258 may be supplied into the reaction chamber 254 together with the carrier gas supplied through the inlet line 268. The inflow of the raw material compound supplied to the reaction chamber 254 through the vaporizer 258 may be controlled by the valve V9.

In addition, as in the deposition devices 200C and 200D illustrated in FIGS. 3C and 3D, a high-frequency power source 292 connected to the reaction chamber 254 is used to generate plasma within the reaction chamber 254 in the thin film forming unit 250. ) and an RF matching system 294.

In the deposition apparatuses 200A, 200B, 200C, and 200D illustrated in FIGS. 3A to 3D, a configuration in which one raw material container 212 is connected to the reaction chamber 254 is illustrated, but the configuration is not limited thereto. If necessary, the fluid transmission unit 210 may be provided with a plurality of raw material containers 212, and each of the plurality of raw material containers 212 may be connected to the reaction chamber 254. The number of raw material containers 212 connected to the reaction chamber 254 is not particularly limited.

In order to vaporize the raw material for forming a metal-containing film containing an organometallic addition compound of general formula (I), a vaporizer 258 is used in any one of the deposition devices 200B and 200D shown in FIGS. 3B and 3D. may be used, but the technical idea of the present invention is not limited thereto.

In order to form a metal-containing film on the substrate according to the manufacturing method of the integrated circuit device described with reference to FIGS. 1 and 2, any one of the deposition devices 200A, 200B, 200C, and 200D shown in FIGS. 3A to 3D is used. Available. For this purpose, an organometallic addition compound according to the technical idea of the present invention having the structure of general formula (I) is transported through various methods to the reaction space of the thin film forming device, for example, the deposition device illustrated in FIGS. 3A to 3D. It can be supplied into the reaction chamber 254 (200A, 200B, 200C, 200D).

In exemplary embodiments, a single wafer facility, such as the deposition apparatuses 200A, 200B, 200C, and 200D illustrated in FIGS. 3A-3D, is used to form a metal-containing film according to the method described with reference to FIGS. 1 and 2. It is also possible to form a metal-containing film on multiple substrates simultaneously using batch-type equipment.

When forming a metal-containing film according to the manufacturing method of an integrated circuit element according to the technical idea of the present invention, conditions for forming the metal-containing film include reaction temperature (substrate temperature), reaction pressure, deposition rate, etc.

The reaction temperature is a temperature at which an organometallic addition compound according to the technical idea of the present invention, for example, an organometallic addition compound having the structure of general formula (I), can sufficiently react, that is, in one example, about 150° C., or The temperature may be selected from the above temperature range, in another example, a temperature of about 150°C to about 400°C, and in another example, a temperature range of about 200°C to about 350°C, but the temperature is not limited to the above examples.

The reaction pressure may be selected in the range of about 10 Pa to atmospheric pressure in the case of a thermal CVD process or optical CVD process, and in the range of about 10 Pa to 2000 Pa in the case of using plasma, but is not limited thereto.

Additionally, the deposition rate can be controlled by adjusting the supply conditions (eg, vaporization temperature and vaporization pressure), reaction temperature, and reaction pressure of the raw material compound. In the thin film forming method according to the technical idea of the present invention, the deposition rate of the metal-containing film is selected within the range of about 0.01 nm/min to about 100 nm/min, for example, about 1 nm/min to about 50 nm/min. However, it is not limited to the above examples. When forming a metal-containing film using an ALD process, the number of ALD cycles can be adjusted to control the metal-containing film of a desired thickness.

According to the technical idea of the present invention, when forming a metal-containing film using an ALD process, energy such as plasma, light, or voltage can be applied. The timing of applying the energy can be selected in various ways. For example, when introducing a source gas containing an organometallic addition compound into the reaction chamber, adsorbing the source gas on the substrate, or during an exhaust process using the purge gas, the reactive gas is released into the reaction chamber. Energy such as plasma, light, or voltage can be applied when introduced, or between each of these points.

According to the technical idea of the present invention, the process of forming a metal-containing film using an organometallic addition compound having the structure of general formula (I) and then annealing in an inert atmosphere, oxidizing atmosphere, or reducing atmosphere may be further included. . Alternatively, in order to fill in the steps formed on the surface of the metal-containing film, a reflow process may be performed on the metal-containing film, if necessary. The annealing process and the reflow process may each be performed under temperature conditions selected within the range of about 200°C to about 1,000°C, for example, about 250°C to about 500°C, but are not limited to the temperatures exemplified above. .

According to the technical idea of the present invention, various types of metals are contained by appropriately selecting the organometallic addition compound according to the technical idea of the present invention, other precursors used with the organometallic addition compound, reactive gas, and thin film formation process conditions. A film can be formed. In exemplary embodiments, the metal-containing film formed according to the spirit of the present invention may include niobium atoms, tantalum atoms, or vanadium atoms. For example, the metal-containing film may include a niobium film, a niobium oxide film, a niobium nitride film, a niobium alloy film, a niobium-containing composite oxide film, a tantalum film, a tantalum oxide film, a tantalum nitride film, a tantalum alloy film, and a tantalum-containing composite oxide film. The niobium alloy film may be made of Nb-Hf alloy, Nb-Ti alloy, etc., but is not limited to the above examples. The tantalum alloy film may be made of Ta-Ti alloy, Ta-W alloy, etc., but is not limited to the above examples. The metal-containing film formed according to the technical idea of the present invention can be used as a material for various components constituting an integrated circuit device. For example, electrode materials for dynamic random-access memory (DRAM) devices, gates and resistors for transistors, diamagnetic films used in hard device recording layers, catalyst materials for solid polymer fuel cells, conductive barrier films used in metal wiring, and capacitors. It can be used in dielectric films, barrier metal films for liquid crystals, thin film solar cell members, semiconductor equipment members, nanostructures, etc., but the use of the metal-containing film is not limited to the above-exemplified devices.

FIGS. 4A to 4J are cross-sectional views shown according to the process sequence to explain the manufacturing method of the integrated circuit device 300 (see FIG. 4J) according to embodiments of the technical idea of the present invention.

Referring to FIG. 4A, after forming an interlayer insulating film 320 on a substrate 310 including a plurality of active regions (AC), an interlayer insulating film 320 is connected to the plurality of active regions (AC) through the interlayer insulating film 320. A plurality of conductive regions 324 are formed.

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

Referring to FIG. 4B, an insulating layer 328 is formed covering 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 be made of an insulating material having an etch selectivity with respect to the interlayer insulating film 320 and the mold film 330 (see FIG. 4C) formed in a subsequent process. The insulating layer 328 may be made of silicon nitride, silicon oxynitride, or a combination thereof.

Referring to FIG. 4C, a mold film 330 is formed on the insulating layer 328.

The mold film 330 may be made of an oxide film. For example, the mold film 330 may include an oxide film such as boro phospho silicate glass (BPSG), phospho silicate glass (PSG), or undoped silicate glass (USG). To form the mold film 130, a thermal CVD process or a plasma CVD process may be used. The mold film 330 may be formed to have a thickness of about 1000 Å to about 20000 Å, but is not limited thereto. In example embodiments, the mold film 330 may include a support film (not shown). The support film may be formed of a material having an etch selectivity with respect to the mold film 330. The support film is a material that has a relatively low etching rate for the etching atmosphere used when removing the mold film 330 in the subsequent process, for example, an etchant containing ammonium fluoride (NH ₄ F), hydrofluoric acid (HF), and water. It can be done. In example embodiments, the support film may be made of silicon nitride, silicon carbonitride, tantalum oxide, titanium oxide, or a combination thereof.

Referring to FIG. 4D, a sacrificial layer 342 and a mask pattern 344 are sequentially formed on the mold layer 330.

The sacrificial film 342 may be made of an oxide film. The mask pattern 344 may be made of an oxide film, a nitride film, a polysilicon film, a photoresist film, or a combination thereof. An area where the lower electrode of the capacitor will be formed may be defined by the mask pattern 344.

Referring to FIG. 4E, the sacrificial layer 342 and the mold layer 330 are dry etched using the mask pattern 344 as an etch mask and the insulating layer 328 as an etch stop layer to form a plurality of holes (H1). ) to form a sacrificial pattern (342P) and a mold pattern (330P) that define the At this time, the insulating layer 328 may also be etched by excessive etching to form an insulating pattern 328P exposing a plurality of conductive regions 324.

Referring to FIG. 4F, after removing the mask pattern 344 from the result of FIG. 4E, a conductive film 350 for forming a lower electrode is formed to fill the plurality of holes H1 and cover the exposed surface of the sacrificial pattern 342P. do.

The conductive film 350 for forming the lower electrode may be made of a doped semiconductor, conductive metal nitride, metal, metal silicide, conductive oxide, or a combination thereof. In example embodiments, the conductive film 350 for forming the lower electrode may be made of a doped semiconductor, a conductive metal nitride, a metal, a metal silicide, a conductive oxide, or a combination thereof. For example, the conductive film 350 for forming the lower electrode is 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, but the constituent material of the conductive film 350 for forming the lower electrode This is not limited to the above examples. To form the conductive film 350 for forming the lower electrode, CVD, MOCVD (metal organic CVD), or ALD processes may be used.

In exemplary embodiments, in order to form the conductive film 350 for forming the lower electrode, a metal-containing film may be formed using process P20 of FIG. 1 or the method described with reference to FIG. 2 . For example, the conductive film 350 for forming the lower electrode may have a multi-layer structure including a TiN film and an NbN film. The NbN film may be a film formed by process P20 of FIG. 1 or the method described with reference to FIG. 2. To form the conductive film 350 for forming the lower electrode, any one of the deposition devices 200A, 200B, 200C, and 200D illustrated in FIGS. 3A to 3D can be used. Referring to FIG. 4G, the upper part of the conductive film 350 for forming the lower electrode is partially removed to form a plurality of lower electrodes LE from the conductive film 350 for forming the lower electrode.

In order to form a plurality of lower electrodes (LE), the upper portion of the conductive film 350 for lower electrode formation is removed using an etchback or CMP (chemical mechanical polishing) process until the upper surface of the mold pattern 330P is exposed. Part of the side and the sacrificial pattern 342P (see FIG. 4F) can be removed.

Referring to FIG. 4H, the mold pattern 330P is removed from the result of FIG. 4G to expose the outer surfaces of the plurality of lower electrodes LE. The mold pattern 330P may be removed by a lift-off process using an etchant containing ammonium fluoride (NH ₄ F), hydrofluoric acid (HF), and water.

Referring to FIG. 4I, a dielectric layer 360 is formed on the plurality of lower electrodes LE.

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

In example embodiments, the dielectric layer 360 is formed of hafnium oxide, hafnium oxynitride, hafnium silicon oxide, zirconium oxide, or 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, but is not limited to the above examples. The dielectric layer 360 may be formed by an ALD process. In example embodiments, to form at least a portion of the dielectric layer 360, a metal-containing layer may be formed using process P20 of FIG. 1 or the method described with reference to FIG. 2 . For example, the dielectric layer 360 may include a tantalum oxide layer, and the tantalum oxide layer may be a layer formed through process P20 of FIG. 1 or the method described with reference to FIG. 2 . To form the dielectric layer 360, any one of the deposition devices 200A, 200B, 200C, and 200D illustrated in FIGS. 3A to 3D can be used. The dielectric layer 360 may have a thickness of about 50 to 150 Å, but is not limited thereto.

In example embodiments, before forming the dielectric layer 360 on the plurality of lower electrodes LE as described with reference to FIG. 4I, a lower interface film (not shown) covering the surface of each of the plurality of lower electrodes LE ) may further include a process of forming. In this case, the dielectric layer 360 may be formed on the lower interface layer. The lower interface layer may be made of a metal-containing layer including niobium, tantalum, or vanadium. To form the metal-containing film constituting the lower interface film, process P20 of FIG. 1 or the method described with reference to FIG. 2 can be used. To form the lower interface film, any one of the deposition devices 200A, 200B, 200C, and 200D shown in FIGS. 3A to 3D can be used.

Referring to FIG. 4J, an upper electrode UE is formed on the dielectric layer 360. The lower electrode LE, the dielectric layer 360, and the upper electrode UE may form a capacitor 370.

The upper electrode UE may be made of a doped semiconductor, conductive metal nitride, metal, metal silicide, conductive oxide, or a combination thereof. For example, the upper electrode (UE) is made of NbN, TiN, TiAlN, TaN, TaAlN, W, WN, Ru, RuO ₂ , SrRuO ₃ , Ir, IrO ₂ , Pt, PtO, SRO(SrRuO ₃ ), BSRO(( It may be made of Ba,Sr)RuO ₃ ), CRO(CaRuO ₃ ), LSCo((La,Sr)CoO ₃ ), or a combination thereof, but is not limited to these. To form the upper electrode (UE), CVD, MOCVD, PVD, or ALD processes can be used.

In exemplary embodiments, a metal-containing film may be formed using process P20 of FIG. 1 or the method described with reference to FIG. 2 to form the upper electrode UE. To form the upper electrode UE, any one of the deposition devices 200A, 200B, 200C, and 200D illustrated in FIGS. 3A to 3D can be used.

In example embodiments, before forming the upper electrode (UE) on the dielectric layer 360 as described with reference to FIG. 4J, a process of forming an upper interface layer (not shown) covering the surface of the dielectric layer 360. It may further include. In this case, the upper electrode UE may be formed on the upper interface layer. The upper interface layer may be made of a metal-containing layer including niobium, tantalum, or vanadium. To form the metal-containing film constituting the upper interface film, process P20 of FIG. 1 or the method described with reference to FIG. 2 can be used. To form the upper interface film, any one of the deposition devices 200A, 200B, 200C, and 200D shown in FIGS. 3A to 3D can be used.

In the method of manufacturing an integrated circuit device described with reference to FIGS. 4A to 4J, the case in which the plurality of lower electrodes LE have a pillar shape has been described as an example, but the technical idea of the present invention is not limited to this. For example, each of the plurality of lower electrodes LE may have a cross-sectional structure of a cup shape or a cylinder shape with a closed bottom.

In the integrated circuit device 300 manufactured by the method described with reference to FIGS. 4A to 4J, the capacitor 370 includes a lower electrode LE having a three-dimensional electrode structure. To compensate for the decrease in capacitance due to the decrease in design rule, the aspect ratio of the lower electrode (LE) of the three-dimensional structure is increasing, and a high-quality dielectric film 360 is installed in a deep and narrow three-dimensional space. An ALD process can be used to form it. According to the manufacturing method of an integrated circuit device according to embodiments of the technical idea of the present invention described with reference to FIGS. 4A to 4J, forming the lower electrode (LE), the dielectric layer 360, or the upper electrode (UE) In this regard, process stability can be improved by using an organometallic addition compound according to the technical idea of the present invention of general formula (I).

Next, specific examples of synthesis of organometallic addition compounds and methods of forming metal-containing films according to embodiments of the technical spirit of the present invention will be described. However, the technical idea of the present invention is not limited to the following examples.

Synthesis Example 1

Synthesis of compounds of formula 2

Under Ar atmosphere, 9.40 g (50.0 mmol) of niobium pentafluoride and 250 ml of dehydrated dichloromethane were added to a 500 mL four-necked flask, the resulting liquid was stirred while maintaining the temperature at 25°C, and then cooled to room temperature. 17.7 g (51.5 mmol) of tris(2,2,2-trifluoroethyl)phosphate was added dropwise and stirred for 5 hours. The solvent and unreacted tris(2,2,2-trifluoroethyl)phosphate were distilled off under reduced pressure, and then purified by distillation to obtain 10.2 g of the target product (yield 38.2%).

(analysis value)

(1) 1H-NMR (heavy benzene)

3.70 ppm (6H, multiplet)

(2) Elemental analysis (theoretical value)

Nb: 17.9% (17.5%), C: 14.0% (13.6%), H: 1.6% (1.1%), F: 50.7% (50.0%), P: 6.1% (5.8%)

Synthesis Example 2

Synthesis of compounds of formula 6

Under Ar atmosphere, 13.5 g (50.0 mmol) of niobium pentachloride and 300 ml of dehydrated dichloromethane were added to a 500 mL four-necked flask, and the resulting liquid was stirred while maintaining the temperature at 25°C, and then incubated with Tris (2) at room temperature. , 17.7 g (51.5 mmol) of 2,2-trifluoroethyl) phosphate was added dropwise and stirred for 5 hours. The solvent and unreacted tris(2,2,2-trifluoroethyl)phosphate were distilled off under reduced pressure, and then purified by distillation to obtain 28.0 g of the target product (yield 91.2%).

(analysis value)

(1) 1H-NMR (heavy benzene)

3.87 ppm(6H, doublet of quarted)

(2) Elemental analysis (theoretical value)

Nb: 15.5% (15.1%), C: 12.0% (11.7%), H: 1.4% (1.0%), Cl: 29.3% (28.9%), F: 28.2% (27.8%), P: 5.1% ( 5.0%)

Synthesis Example 3

Synthesis of compounds of formula 7

Under Ar atmosphere, 13.5 g (50.0 mmol) of niobium pentachloride and 300 ml of dehydrated dichloromethane were added to a 500 mL four-necked flask, and the resulting liquid was stirred while maintaining the temperature at 25°C, and then added to Tris (1,1,1) at room temperature. , 28.2 g (51.5 mmol) of 3,3,3-hexafluoro-2-propyl) phosphate (tris (1,1,1,3,3,3-hexafluoro-２-propyl) phosphate) was added dropwise and incubated for 5 hours. It was stirred. The solvent and unreacted tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphate were distilled off under reduced pressure, and then purified by distillation to obtain 20.5 g of the target product (yield 50.2%).

(analysis value)

(1) 1H-NMR (heavy benzene)

4.81 ppm (3H, singlet, broad)

(2) Elemental analysis (theoretical value)

Nb: 11.5% (11.4%), C: 13.5% (13.2%), H: 0.8% (0.4%), Cl: 22.0% (21.7%), F: 42.0% (41.8%), P: 4.1% ( 3.8%)

Synthesis Example 4

Synthesis of compounds of formula 14

Under Ar atmosphere, 17.9 g (50.0 mmol) of TaCl ₅ and 300 ml of dehydrated dichloromethane were added to a 500 mL four-necked flask, and the resulting liquid was stirred while maintaining the temperature at 25°C. Then, Tris (2,2,2- 17.7 g (51.5 mmol) of trifluoroethyl) phosphate was added dropwise and stirred for 5 hours. The solvent and unreacted tris(2,2,2-trifluoroethyl)phosphate were distilled off under reduced pressure, and then purified by distillation to obtain 30.9 g of the target product (yield 87.9%).

(analysis value)

(1) 1H-NMR (heavy benzene)

3.85 ppm(6H, doublet of quarted)

(2) Elemental analysis (theoretical value)

Ta: 25.9% (25.8%), C: 10.7% (10.3%), H: 1.1% (0.9%), Cl: 25.7% (25.2%), F: 24.6% (24.4%), P: 4.4% ( 4.4%)

Comparative evaluation examples 1 to 4 with evaluation examples 1 to 4

Next, the compounds of Formula 2, Formula 6, Formula 7, and Formula 14 obtained in Synthesis Examples 1 to 4, and Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4 shown below, respectively, were subjected to normal pressure. TG-DTA (Thermogravimetry - Differential Thermal Analysis) 50% mass reduction temperature (T1), state at 25°C, and melting point were evaluated as follows.

Comparative Compound 1

Comparative Compound 2

Comparative Compound 3

Comparative Compound 4

In Comparative Compound 4 above, the abbreviation “nBu” refers to a normal butyl group.

(1) Normal pressure TG-DTA evaluation

Using TG-DTA, under normal pressure, the Ar flow rate was 100 mL/min, the temperature increase rate was 10 °C/min, and the scanning temperature range was 30 °C to 600 °C, using Equations 2 and 6 obtained in Synthesis Examples 1 to 4, The 50% mass reduction temperature (T1) of the compounds of Formula 7 and Formula 14 and Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4 were measured, and the results are shown in Table 1.

(2) Melting point evaluation

State of the compounds at 25°C for the compounds of Formula 2, Formula 6, Formula 7, and Formula 14 obtained in Synthesis Examples 1 to 4, and Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4, respectively. was observed with the naked eye, the melting point of the solid material was measured at 25°C, and the results are shown in Table 1.

Evaluation example metal type compound T1
(℃) Condition at 25℃ melting point
(℃) Evaluation example 1 Nb Equation 2 181 Liquid - Evaluation example 2 Equation 6 210 Liquid - Evaluation example 3 Equation 7 150 Liquid - Comparative evaluation example 1 Comparative Compound 1 184 solid 205 Comparative evaluation example 2 Comparative Compound 2 379 solid 359 Evaluation example 4 Ta Equation 14 215 Liquid - Comparative evaluation example 3 Comparative Compound 3 181 solid 220 Comparative evaluation example 4 Comparative Compound 4 245 solid 119

From the results in Table 1, it was confirmed that the compounds of Equation 2, Equation 6, Equation 7, and Equation 14 were all compounds with relatively high vapor pressures, with the atmospheric pressure TG-DTA mass reduction temperature (T1) of 50% being about 215°C or less. In addition, it was confirmed that the compounds of Formula 2, Formula 6, Formula 7, and Formula 14 were all liquid at 25°C and had melting points lower than 25°C.

On the other hand, it was confirmed that Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4 each had a relatively high melting point of 115°C or higher. Comparative Compound 1 and Comparative Compound 3 have a 50% reduction temperature (T1) of TG-DTA mass at normal pressure around 180°C, and are compounds with relatively high vapor pressures similar to the compounds according to the present invention, but their melting points are significantly above 205°C. It was confirmed that it was at a high level.

Comparative evaluation examples 5 to 8 Evaluation examples 5 to 8 (metal-containing film formation)

Next, the compounds of Formula 2, Formula 6, Formula 7, and Formula 14 obtained in Synthesis Examples 1 to 4, and Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4, respectively, were used as raw materials, A niobium nitride film was formed on a silicon substrate using the deposition apparatus of FIG. 3A. ALD process conditions for forming the niobium nitride film were as follows.

(condition)

Reaction temperature (substrate temperature): 250 ℃

Reactive Gas: Ammonia Gas

(process)

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

Process (1): A process of introducing the vaporized raw material into the chamber under the conditions of a raw material container heating temperature of 90°C and an internal pressure of the raw material container of 100 Pa and depositing it for 30 seconds at a pressure within the chamber of 100 Pa.

Process (2): A process of removing unreacted raw materials by Ar purge for 10 seconds.

Process (3): Supplying reactive gas and reacting at a chamber pressure of 100 Pa for 30 seconds.

Process (4): A process of removing unreacted raw materials by Ar purge for 10 seconds.

The thickness of each thin film obtained through the above process was measured by X-ray reflectivity method, the compound of each thin film obtained by X-ray diffraction method was confirmed, and the carbon content of each thin film obtained by The results are shown in Table 2.

Evaluation example compound thin film thickness
(nm) thin film compounds carbon content Evaluation example 5 Equation 2 5.5 NbN Not detected Evaluation example 6 Equation 6 8.5 NbN Not detected Evaluation example 7 Equation 7 5.0 NbN Not detected Comparative evaluation example 5 Comparative Compound 1 2.5 NbN Not detected Comparative evaluation example 6 Comparative Compound 2 3.0 NbN 6 atomic% Evaluation example 8 Equation 14 8.0 TaN Not detected Comparative evaluation example 7 Comparative Compound 3 2.0 TaN Not detected Comparative evaluation example 8 Comparative Compound 4 2.5 TaN 7 atomic%

From the results in Table 2, among the thin films obtained by the ALD method, the thin films obtained from Comparative Compound 2 and Comparative Compound 4 each had a carbon content of 6 atomic% or more. On the other hand, the thin films obtained from the compounds of Equation 2, Equation 6, Equation 7, and Equation 14 were confirmed to be high quality thin films with a detection limit of 0.1 atomic% or less. In addition, as a result of evaluating the thickness of the thin films obtained after performing 150 cycles of the ALD process, it was 3 nm or less for Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4, whereas Equations 2, 6, The thin films obtained from the compounds of Equation 7 and Equation 14 were 5.0 nm or larger, confirming that the productivity of the thin film formation process was excellent.

As confirmed from the above evaluation examples, organometallic addition compounds according to the technical spirit of the present invention have a low melting point and high vapor pressure, and can increase the productivity of thin film formation when used as a raw material for thin film formation by an ALD or CVD process.

Above, the present invention has been described in detail with preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications and changes can be made by those skilled in the art within the technical spirit and scope of the present invention. This is possible.

310: substrate, 360: dielectric film, 370: capacitor, LE: lower electrode, UE: upper electrode.

Claims (20)

Organometallic addition compounds of the following general formula (I):
General formula (I)

In general formula (I),
R ¹ , R ² , and R ³ are each independently a C1-C5 alkyl group, and at least one of R ¹ , R ² , and R ³ has at least two hydrogen atoms in the alkyl group replaced with fluorine atoms,
M is a niobium atom, a tantalum atom, or a vanadium atom,
X is a halogen atom,
m is an integer from 3 to 5,
n is 1 or 2. According to paragraph 1,
An organometallic addition compound in which at least one of R ¹ , R ² , and R ³ is a straight-chain alkyl group. According to paragraph 1,
An organometallic addition compound wherein at least one of R ¹ , R ² , and R ³ is a branched alkyl group. According to paragraph 1,
In general formula (I), M is a niobium atom or a tantalum atom,
An organometallic addition compound where X is a fluorine atom or a chlorine atom. According to paragraph 1,
R ¹ , R ² , and R ³ are each independently a trifluoromethyl group, a trifluoroethyl group, a hexafluoroisopropyl group, or a nonafluoro tert-butyl group. According to paragraph 1,
In general formula (I), m is 5 and n is 1. According to paragraph 1,
In general formula (I), M is a niobium atom or a tantalum atom,
X is a chlorine atom,
An organometallic addition compound in which R ¹ , R ² , and R ³ are each a branched alkyl group. According to paragraph 1,
In general formula (I), M is a niobium atom or a tantalum atom,
X is a fluorine atom,
An organometallic addition compound in which R ¹ , R ² , and R ³ are each a branched alkyl group. According to paragraph 1,
In general formula (I), M is a niobium atom or a tantalum atom,
X is a chlorine atom,
R ¹ , R ² , and R ³ are each organometallic addition compounds in which all hydrogen atoms contained in the alkyl group are replaced with fluorine atoms. According to paragraph 1,
In general formula (I), M is a niobium atom or a tantalum atom,
X is a fluorine atom,
R ¹ , R ² , and R ³ are each organometallic addition compounds in which all hydrogen atoms contained in the alkyl group are replaced with fluorine atoms. According to paragraph 1,
The compound of general formula (I) is an organometallic addition compound that is liquid at room temperature. A method of manufacturing an integrated circuit device comprising forming a metal-containing film on a substrate using an organometallic addition compound of the following general formula (I).
General formula (I)

In general formula (I),
R ¹ , R ² , and R ³ are each independently a C1-C5 alkyl group, and at least one of R ¹ , R ² , and R ³ has at least one hydrogen atom contained in the alkyl group replaced with a fluorine atom,
M is a niobium atom, a tantalum atom, or a vanadium atom,
X is a halogen atom,
m is an integer from 3 to 5,
n is 1 or 2. According to clause 12,
A method of manufacturing an integrated circuit device in which the organometallic addition compound is liquid at room temperature. According to clause 12,
In general formula (I), M is a niobium atom or a tantalum atom,
A method of manufacturing an integrated circuit element where X is a fluorine atom or a chlorine atom. According to clause 12,
R ¹ , R ² , and R ³ are each independently a trifluoromethyl group, a trifluoroethyl group, a hexafluoroisopropyl group, or a nonafluoro tert-butyl group. According to clause 12,
In general formula (I), m is 5 and n is 1. A method of manufacturing an integrated circuit element. According to clause 12,
The step of forming the metal-containing film is
supplying a compound of general formula (I) onto the substrate;
A method of manufacturing an integrated circuit device comprising supplying a reactive gas onto the substrate. According to clause 17,
The reactive gas is NH ₃ , N ₂ plasma, an organic amine compound, a hydrazine compound, or a combination thereof. According to clause 17,
The reactive gases include O ₂ , O ₃ , O ₂ plasma, H ₂ O, NO ₂ , NO, N ₂ O (nitrous oxide), CO, CO ₂ , H ₂ O ₂ , HCOOH, CH ₃ COOH, (CH ₃ CO) ₂ A method of manufacturing an integrated circuit device selected from O, alcohol, peroxide, sulfur oxide, or a combination thereof. According to clause 17,
A method of manufacturing an integrated circuit device wherein the reactive gas is H ₂ .

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