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

general formula (I)

Wherein, in the general formula (I),

R¹、R²and R³Each independently is C1 to C5 alkyl, R¹、R²And R³Is a C1 to C5 alkyl group in which at least one hydrogen atom is substituted by a fluorine atom,

m is niobium atom, tantalum atom or vanadium atom,

x is a halogen atom, and X is a halogen atom,

m is an integer of 3 to 5, and

n is 1 or 2.

2. The organometallic addition compound of claim 1 wherein R¹、R²And R³At least one of which is a linear C1 to C5 alkyl group.

3. The organometallic addition compound of claim 1 wherein R¹、R²And R³At least one of which is a branched C3 to C5 alkyl group.

4. An organometallic addition compound according to claim 1, wherein in the general formula (I):

m is a niobium atom or a tantalum atom, and

x is a fluorine atom or a chlorine atom.

5. The organometallic addition compound of claim 1 wherein R¹、R²And R³Each independently trifluoromethyl, trifluoroethyl, hexafluoroisopropyl, or nonafluorotert-butyl.

6. The organometallic addition compound according to claim 1, wherein in the general formula (I), m is 5 and n is 1.

7. An organometallic addition compound according to claim 1, wherein in the general formula (I):

m is a niobium atom or a tantalum atom,

x is a chlorine atom, and

R¹、R²and R³Each independently a branched C3 to C5 alkyl group.

8. An organometallic addition compound according to claim 1, wherein in the general formula (I):

m is a niobium atom or a tantalum atom,

x is a fluorine atom, and

R¹、R²and R³Each independently a branched C3 to C5 alkyl group.

9. An organometallic addition compound according to claim 1, wherein in the general formula (I):

m is a niobium atom or a tantalum atom,

x is a chlorine atom, and

R¹、R²and R³Each independently is a C1 to C5 alkyl group in which all hydrogen atoms are substituted with fluorine atoms.

10. An organometallic addition compound according to claim 1, wherein in the general formula (I):

m is a niobium atom or a tantalum atom,

x is a fluorine atom, and

R¹、R²and R³Each independently is a C1 to C5 alkyl group in which all hydrogen atoms are substituted with fluorine atoms.

11. The organometallic addition compound of claim 1 wherein the organometallic addition compound is a liquid at 20 ℃ to 28 ℃.

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

general formula (I)

Wherein, in the general formula (I),

R¹、R²and R³Each independently is C1 to C5 alkyl, R¹、R²And R³Is a C1 to C5 alkyl group in which at least one hydrogen atom is substituted by a fluorine atom,

m is niobium atom, tantalum atom or vanadium atom,

x is a halogen atom, and X is a halogen atom,

m is an integer of 3 to 5, and

n is 1 or 2.

13. The method of claim 12, wherein the organometallic addition compound is a liquid at 20 ℃ to 28 ℃.

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

m is a niobium atom or a tantalum atom, and

x is a fluorine atom or a chlorine atom.

15. The method of claim 12, wherein R¹、R²And R³Each independently trifluoromethyl, trifluoroethyl, hexafluoroisopropyl, or nonafluorotert-butyl.

16. The process according to claim 12, wherein, in the general formula (I), m is 5 and n is 1.

17. The method of claim 12, wherein forming a metal-containing film comprises:

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

a reactive gas is supplied onto the substrate.

18. The method of claim 17, wherein the reactive gas comprises NH₃、N₂Plasma, organic amine compounds, hydrazine compounds, or combinations thereof.

19. The method of claim 17, wherein the reactive gas comprises O₂、O₃、O₂Plasma, H₂O、NO₂、NO、N₂O、CO、CO₂、H₂O₂、HCOOH、CH₃COOH、(CH₃CO)₂O, alcohol, peroxide, sulfur oxide, or combinations thereof.

20. The method of claim 17, wherein the reactive gas comprises H₂。

Background

In recent years, due to the rapid progress in the downsizing of semiconductor devices due to the development of electronic technology, patterns included in electronic devices have been miniaturized.

Disclosure of Invention

Embodiments may be realized by providing an organometallic addition compound represented by general formula (I):

general formula (I)

Wherein, in the general formula (I), R¹、R²And R³Each independently is C1 to C5 alkyl, R¹、R²And R³At least one of which is a C1 to C5 alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, M is a niobium atom, a tantalum atom or a vanadium atom, X is a halogen atom, M is an integer of 3 to 5, and n is 1 or 2.

Embodiments may be realized by providing a method of manufacturing an Integrated Circuit (IC) device, the method comprising forming a metal-containing film on a substrate using an organometallic addition compound represented by general formula (I),

general formula (I)

Wherein, in the general formula (I), R¹、R²And R³Each independently is C1 to C5 alkyl, R¹、R²And R³At least one of which is a C1 to C5 alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, M is a niobium atom, a tantalum atom or a vanadium atom, X is a halogen atom, M is an integer of 3 to 5, and n is 1 or 2.

Drawings

Features of the present application 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 (IC) device according to an embodiment;

fig. 2 is a detailed flowchart of a method of forming a metal-containing film by using a method of manufacturing an IC device according to an exemplary embodiment;

FIGS. 3A through 3D are schematic diagrams of configurations of deposition systems that may be used to form metal-containing films in methods of fabricating IC devices according to example embodiments; and

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

Detailed Description

When the term "substrate" is used herein, it should be understood as the substrate itself, or a stacked structure including the substrate and a predetermined layer or film formed on a surface of the substrate. When the term "surface of the substrate" is used herein, it is to be understood as an exposed surface of the substrate itself, or an outer surface of a predetermined layer or film formed on the substrate. As used herein, the term "room temperature" or "ambient temperature" refers to a temperature in the range of about 20 ℃ to about 28 ℃, and may vary depending on the season.

The organometallic addition compound according to the embodiment may have a structure in which an organophosphate group is bonded to a complex metal compound in the form of an adduct. The organometallic addition compound according to the embodiment may be represented by the following general formula (I).

General formula (I)

In the general formula 1, R¹、R²And R³Each may independently be or include, for example, a C1 to C5 alkyl group (e.g., a substituted or unsubstituted C1 to C5 alkyl group). In one embodiment, R¹、R²And R³May be a C1 to C5 alkyl group in which at least one hydrogen atom is substituted or replaced by a fluorine atom. M may be an element selected from group V of the periodic table (for example, a niobium atom, a tantalum atom, or a vanadium atom), X may be a halogen atom, M may be an integer of 3 to 5, and n may be 1 or 2. As used herein, the term "or" is not an exclusive term, e.g., "A or B" will includeIncluding A, B, or A and B.

In one embodiment, R¹、R²And R³At least one of which may be a straight chain alkyl group (e.g., a straight chain C1 to C5 alkyl group). In one embodiment, R¹、R²And R³At least one of which may be a branched alkyl (e.g., branched C3 to C5 alkyl).

In one embodiment, R¹、R²And R³May each independently be or include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl or tert-pentyl.

In one embodiment, R¹、R²And R³May each independently be or include, for example, trifluoromethyl, trifluoroethyl, hexafluoroisopropyl or nonafluorotert-butyl.

In the general formula (I), X may be a fluorine (F) atom, a chlorine (Cl) atom, a bromine (Br) atom or an iodine (I) atom. When X is a fluorine atom or a chlorine atom, the melting point of the organometallic addition compound can be further lowered, and the vapor pressure of the organometallic addition compound can be further raised.

The organometallic addition compounds according to embodiments may be liquid at room temperature. When the organometallic addition compound is liquid at room temperature, the organometallic addition compound can be easily handled. In the general formula (I), when R is¹、R²And R³When at least one of them is a branched alkyl group, the organometallic addition compound can advantageously be placed in or be in the liquid phase at room temperature. In one embodiment, the organometallic addition compound can be a liquid at room temperature at atmospheric pressure (e.g., 1atm) or under pressure conditions that ensure that the compound is in a liquid phase.

In one embodiment, in the 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 one embodiment, in formula (I), m may be 5 and n may be 1.

In a fruitIn the general formula (I), M may be a niobium atom or a tantalum atom, X may be a chlorine atom, and R¹、R²And R³May each independently be a branched alkyl group.

In one embodiment, in the general formula (I), M may be a niobium atom or a tantalum atom, X may be a fluorine atom, and R¹、R²And R³May each independently be a branched alkyl group.

In one embodiment, in the general formula (I), M may be a niobium atom or a tantalum atom, X may be a chlorine atom, and R¹、R²And R³May each independently be an alkyl group in which all hydrogen atoms are substituted with fluorine atoms (e.g., a C1 to C5 perfluoroalkyl group).

In one embodiment, in the general formula (I), M may be a niobium atom or a tantalum atom, X may be a fluorine atom, and R¹、R²And R³May each independently be an alkyl group in which all hydrogen atoms are substituted with fluorine atoms.

The organometallic addition compound according to one embodiment may have a structure in which an organophosphate group is bonded to a complex metal compound in the form of an adduct. The organometallic addition compounds can be used as precursors to metals during the formation of metal-containing films using Chemical Vapor Deposition (CVD) processes or Atomic Layer Deposition (ALD) processes. In this case, the organophosphate group may protect the coordinated metal compound through a coordinate bond when the organometallic addition compound is stored in the container. In addition, when the organometallic addition compound is delivered to the deposition reaction chamber for forming the metal-containing film, the organometallic addition compound may be easily decomposed due to the process temperature in the deposition reaction chamber, and may not affect the surface reaction for forming the metal-containing film.

In one embodiment, the organometallic addition compound may be represented by one of the following formulas 1 to 16.

The organometallic addition compounds can be prepared by utilizing suitable reactions. For example, a solution may be obtained by reacting niobium pentachloride with a phosphate ester having a structure corresponding to the final structure to be synthesized at a temperature of about 25 ℃ in a dichloromethane solvent, and distilling the solvent and unreacted products from the solution. Thereafter, the organometallic addition compounds according to embodiments can be synthesized by using distillation and purification methods.

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

Fig. 1 is a flow diagram of a method of manufacturing an Integrated Circuit (IC) device, according to an embodiment.

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

The substrate may comprise silicon, ceramic, glass, metal nitride, or combinations thereof. The ceramic may include silicon nitride, titanium nitride, tantalum nitride, titanium oxide, niobium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, or combinations thereof. Each of the metal and the metal nitride may include titanium (Ti), tantalum (Ta), cobalt (Co), ruthenium (Ru), zirconium (Zr), hafnium (Hf), lanthanum (La), or a combination thereof. The surface of the substrate may have a flat, spherical, fibrous or scaly shape. In one embodiment, the surface of the substrate may have a three-dimensional (3D) structure, such as a trench structure or the like.

In one embodiment, the substrate may have the same configuration as the substrate 310 described below with reference to fig. 4A.

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

The source for forming the metal-containing film may comprise an organometallic addition compound according to an embodiment. In one embodiment, the source for forming the metal-containing film may include at least one of the organometallic addition compounds represented by formulas 1 to 16. In one embodiment, the organometallic addition compound may be a liquid at room temperature.

The source for forming the metal-containing film may vary, and may be selected, for example, according to the thin film to be formed. In one embodiment, the metal-containing film that is intended to be formed may include a niobium-containing film, a tantalum-containing film, or a vanadium-containing film. When a niobium-containing film is to be formed, an organometallic addition compound of the general formula (I) in which M is a niobium atom can be used as a source for forming a metal-containing film. When a tantalum-containing film is to be formed, an organometallic addition compound of the general formula (I) in which M is a tantalum atom can be used as a source for forming the metal-containing film. When a vanadium-containing film is to be formed, an organometallic addition compound of the general formula (I) in which M is a vanadium atom can be used as a source for forming the metal-containing film. In this case, the source for forming the metal-containing film may contain only the organometallic addition compound according to the embodiment, and may not contain other metal compounds and semimetal compounds.

In one embodiment, the metal-containing film intended to be formed may also contain other metals besides niobium, tantalum, or vanadium. In one embodiment, when the metal-containing film to be formed is a film further containing other metal or semimetal than niobium, tantalum, or vanadium, the source for forming the metal-containing film may further contain a compound containing the desired metal or semimetal (hereinafter referred to as "other precursor") in addition to the organometallic addition compound according to the embodiment. In one embodiment, the source for forming the metal-containing film may comprise an organic solvent or nucleophile in addition to the organometallic addition compound according to an embodiment.

According to process P20 of fig. 1, a metal-containing film may be formed using a CVD process or an ALD process. The source for forming a metal-containing film comprising the organometallic addition compound according to embodiments may be suitable for use in a chemical deposition process, such as a CVD process or an ALD process.

When the source for forming the metal-containing film is used in the electroless deposition process, the composition of the source for forming the metal-containing film may be appropriately selected according to the method of delivery. As the method of conveyance, a gas conveyance method or a liquid conveyance method may be used. When the gas delivery method is used, the source for forming the metal-containing film may be evaporated to generate vapor by heating and/or reducing pressure in a storage container (hereinafter referred to as "source container") in which the source for forming the metal-containing film is stored. The vapor may be introduced into a chamber in which the substrate is loaded (hereinafter referred to as "deposition chamber") together with a carrier gas (e.g., argon, nitrogen, or helium) used as necessary. When the liquid delivery method is used, the source for forming the metal-containing film may be delivered to the evaporator in a liquid state or a solution state, and heated and/or depressurized and evaporated in the evaporator to generate a vapor, which may be introduced into the deposition chamber.

When the metal-containing film is formed using the gas delivery method according to process P20 of fig. 1, the organometallic addition compound represented by general formula (I) itself can be used as a source for forming the metal-containing film. When the metal-containing film is formed using the liquid delivery method according to process P20 of fig. 1, the organometallic addition compound represented by general formula (I) itself or a solution in which the organometallic addition compound of general formula (I) is dissolved in an organic solvent may be used as a source for forming the metal-containing film. The source used to form the metal-containing film may also comprise other precursors, nucleophiles, and the like.

In one embodiment, a metal-containing film may be formed using a multi-component CVD process in a method of manufacturing an IC device according to an embodiment. The multi-component CVD process may be performed by using the following method: a method of independently evaporating and supplying each component of the source for forming the metal-containing film (hereinafter referred to as "single source method"), or a method of evaporating and supplying a source mixture obtained by mixing multi-component sources in a desired composition in advance (hereinafter referred to as "cocktail source method"). When the cocktail source method is used, a mixture of the organometallic addition compound and other precursors according to the embodiment or a mixed solution obtained by dissolving the mixture in an organic solvent may be used as a source for forming a metal-containing film. The mixture or mixed solution may also contain a nucleophile.

The above organic solvent may include suitable organic solvents, for example: acetates such as ethyl acetate, n-butyl acetate and methoxyethyl acetate; ethers such as tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and dibutyl ether; ketones, such as dibutyl ketone, diethyl butyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone; hydrocarbons such as hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, toluene and xylene; hydrocarbons having a cyano group such as 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1, 3-dicyanopropane, 1, 4-dicyanobutane, 1, 6-dicyanohexane, 1, 4-dicyanocyclohexane and 1, 4-dicyanobenzene; pyridine; or lutidine. The organic solvent may be used alone or as a mixture of at least two thereof in consideration of the relationship between the solubility of the solute, the use temperature, the boiling point and the ignition point.

When an organic solvent is included in the source for forming a metal-containing film including the organometallic addition compound according to the embodiment, the total amount of the organometallic addition compound according to the embodiment and the other precursor in the organic solvent may be in a range of about 0.01mol/L to about 2.0mol/L, for example, about 0.05mol/L to about 1.0 mol/L. Here, the total amount means the amount of the organometallic addition compound according to the embodiment when the source for forming the metal-containing film does not contain the metal compound and the semimetal compound other than the organometallic addition compound according to the embodiment, and means the sum of the amounts of the organometallic addition compound and the other precursor according to the embodiment when the source for forming the metal-containing film contains the organometallic addition compound and the other metal compound or semimetal compound (i.e., other precursor) according to the embodiment.

In the method of manufacturing an IC device according to an embodiment, when a metal-containing film is formed using a multi-component CVD process, other precursors that may be used with the organometallic addition compound according to an embodiment may include precursors suitable for forming metal-containing films.

In one embodiment, other precursors that may be used to form a metal-containing film in the method of manufacturing an IC device according to an embodiment may include a complex of silicon and a metal, at least one organic complex compound of an alcohol compound, a glycol compound, a β -diketone compound, a cyclopentadiene compound, and an organic amine compound.

Other precursors may include: for example, lithium (Li), sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti), zirconium (Zr), hafnium (Hf), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), aluminum (Al), gallium (Ga), indium (In), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) or lutetium (Lu).

Alcohol compounds that may be used as organic coordination compounds for other precursors may include: for example, alkyl alcohols such as methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, isobutanol, tert-butanol, pentanol, isopentyl alcohol, and tert-pentanol; ether alcohols, such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2- (2-methoxyethoxy) ethanol, 2-methoxy-1-methylethanol, 2-methoxy-1, 1-dimethylethanol, 2-ethoxy-1, 1-dimethylethanol, 2-isopropoxy-1, 1-dimethylethanol, 2-butoxy-1, 1-dimethylethanol, 2- (2-methoxyethoxy) -1, 1-dimethylethanol, 2-propoxy-1, 1-diethylethanol, 2-sec-butoxy-1, 1-diethylethanol, and 3-methoxy-1, 1-dimethylpropanol; and dialkylamino alcohols such as dimethylaminoethanol, ethylmethylaminoethanol, diethylaminoethanol, dimethylamino-2-pentanol, ethylmethylamino-2-pentanol, dimethylamino-2-methyl-2-pentanol, ethylmethylamino-2-methyl-2-pentanol and diethylamino-2-methyl-2-pentanol.

The diol compounds that may be used as the organic complex compounds of the other precursors may include: for example, 1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 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.

The beta-diketone compounds that can be used as organic complex compounds of other precursors may include: for example, 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, 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; fluoro-substituted alkyl β -diketones, such as 1,1, 1-trifluoropentane-2, 4-dione, 1,1, 1-trifluoro-5, 5-dimethylhexane-2, 4-dione, 1,1,1,5,5, 5-hexafluoropentane-2, 4-dione and 1, 3-diperfluorohexylpropane-1, 3-dione; and ether-substituted β -diketones such as 1,1,5, 5-tetramethyl-1-methoxyhexane-2, 4-dione, 2,6, 6-tetramethyl-1-methoxyheptane-3, 5-dione and 2,2,6, 6-tetramethyl-1- (2-methoxyethoxy) heptane-3, 5-dione.

Cyclopentadiene compounds that can be used as organic coordination compounds for other precursors can include: for example, cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, sec-butylcyclopentadiene, isobutylcyclopentadiene, tert-butylcyclopentadiene, dimethylcyclopentadiene, and tetramethylcyclopentadiene.

Organic amine compounds that may be used as organic coordination compounds for other precursors may include: for example, methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, ethylmethylamine, propylmethylamine and isopropylmethylamine.

Other precursors may be suitable materials, and methods of making the other precursors may be suitable methods. In one 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 corresponding alcohol compound. In one embodiment, the inorganic salt of the above element or a hydrate thereof may include, for example, a metal halide or a metal nitrate. The alkali metal alkoxide may include, for example, sodium alkoxide, lithium alkoxide, and potassium alkoxide.

When a single source process is used, the other precursors may comprise compounds similar in thermal and/or oxidative decomposition behavior to the organometallic addition compounds according to embodiments. When the cocktail source method is used, the other precursors may include materials similar in thermal and/or oxidative decomposition behavior to the organometallic addition compounds according to embodiments, and may not deteriorate due to chemical reactions upon mixing with the organometallic addition compounds according to embodiments.

In one embodiment, to form a metal-containing film using the method of manufacturing an IC device according to an embodiment, a source for forming the metal-containing film may include a nucleophile. The nucleophile may provide stability to organometallic addition compounds and/or other precursors that include niobium, tantalum, or vanadium atoms according to embodiments. Nucleophiles may include: for example, glycol ethers such as glyme, diglyme, triglyme, and tetraglyme; crown ethers such as 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8 and dibenzo-24-crown-8; polyamines, such as ethylenediamine, N' -tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,4,7, 7-pentamethyldiethylenetriamine, 1,4,7,10, 10-hexamethyltriethylenetetramine, and triethoxytriethylenamine; cyclic polyamines such as cyclam and cyclen; heterocyclic compounds, e.g. pyridine, pyrrolidine, piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1, 4-bisAn alkyl, an aryl,Azole, thiazole and oxathiolane (oxathiol)ane); beta-ketoesters, such as methyl acetoacetate, ethyl acetoacetate, 2-methoxyethyl acetoacetate; or beta-diketones such as acetylacetone, 2, 4-hexanedione, 2, 4-heptanedione, 3, 5-heptanedione, and dipivaloylmethane. The nucleophile may be used in an amount of about 0.1mol to about 10mol, for example about 1mol to about 4mol, based on the total amount of 1mol of precursor.

In the source for forming a metal-containing film by using the method for manufacturing an IC device according to the embodiment, it may be useful to suppress the amounts of an impurity metal element, an impurity halogen (e.g., impurity chlorine), and an impurity organic material as much as possible. In one embodiment, one metal may be contained as an impurity metal element in an amount of about 100ppb or less in a source for forming a metal-containing film. In one embodiment, one metal may be contained as an impurity metal element in an amount of about 10ppb or less in a source for forming a metal-containing film. In one embodiment, the total amount of impurity metals may be included in the source for forming the metal-containing film in an amount of about 1ppm or less, for example about 100ppb or less. In one embodiment, when forming a metal-containing film used as a gate insulating film, a gate conductive film, or a barrier film constituting a Large Scale Integration (LSI) device, it may be useful to minimize the contents of alkali metal elements and alkaline earth metal elements, which affect the electrical characteristics of the resulting film. In one embodiment, the impurity halogen component may be included in the source for forming the metal-containing film in an amount of about 100ppm or less, such as about 10ppm or less or about 1ppm or less.

The impurity organic component may be included in the source for forming the metal-containing film in an amount of about 500ppm or less, for example, about 50ppm or less or about 10ppm or less, based on the total amount of the source for forming the metal-containing film.

In the source for forming the metal-containing film, moisture may cause particles in the source for forming the metal-containing film, or particles during the thin film forming process. In one embodiment, the moisture of each of the precursor, organic solvent, and nucleophile may be removed prior to its use. The moisture content of each of the precursor, organic solvent, and nucleophile may be less than about 10ppm, for example less than about 1 ppm.

When the metal-containing film is formed by using the method of manufacturing an IC device according to the embodiment, the content of particles in the source for forming the metal-containing film can be minimized to reduce contamination of the metal-containing film to be formed by the particles. In one embodiment, when measuring particles in a liquid state by using a light scattering type particle detector, the number of particles having a size of more than about 0.3 μm in 1ml of liquid can be adjusted to 100 or less. In one embodiment, the number of particles having a size greater than about 0.2 μm may be adjusted to below 1,000, and in one example to below 100, in 1ml of liquid.

In process P20 of FIG. 1, forming the metal-containing film using the source for forming the metal-containing film may include: a process of evaporating a source for forming a metal-containing film, introducing the source for forming the metal-containing film into a deposition reactor in which a substrate is loaded, and depositing the source for forming the metal-containing film on a surface of the substrate to form a precursor thin film on the substrate, and a process of reacting the precursor thin film with a reactive gas to form the metal-containing film containing niobium atoms, tantalum atoms, or vanadium atoms on the surface of the substrate.

In order to evaporate the source for forming the metal-containing film and introduce the source for forming the metal-containing film into the deposition reactor, the above-described gas delivery method, liquid delivery method, single source method, or cocktail source method, or the like may be used.

The reactive gas may be a gas that reacts with the precursor film. In one embodiment, the reactive gas may include an oxidizing gas, a reducing gas, or a nitriding gas.

The oxidizing gas may include: e.g. O₂、O₃、O₂Plasma, H₂O、NO₂、NO、N₂O、CO、CO₂、H₂O₂、HCOOH、CH₃COOH、(CH₃CO)₂O, alcohol, peroxide, sulfur oxide, or combinations thereof.

The reducing gas may include, for example, H₂。

The nitriding gas may include: for example, NH₃、N₂Plasma, monoalkylamine, dialkylamine, trialkylamine, organic amine compounds (e.g., alkylene diamine), hydrazine compounds, or combinations thereof.

When the metal oxide film containing niobium atoms, tantalum atoms, or vanadium atoms is formed in process P20 of fig. 1, an oxidizing gas may be used as the reactive gas. When the metal nitride film containing niobium atoms, tantalum atoms, or vanadium atoms is formed in process P20 of fig. 1, a nitriding gas may be used as the reactive gas.

In one embodiment, in process P20 of fig. 1, a metal-containing film containing niobium atoms, tantalum atoms, or vanadium atoms may be formed by using the following process: a thermal CVD process of forming a thin film by allowing a source gas containing an organometallic addition compound according to an embodiment or both of the source gas and a reactive gas to react only by heating, a plasma CVD process using heating and plasma, a photo CVD process using heating and light, a photo-plasma CVD process using heating, light, and plasma, or an ALD process.

When the metal-containing film is formed according to the process P20 of fig. 1, the reaction temperature (or substrate temperature), the reaction pressure, the deposition rate, and the like may be appropriately selected according to the desired thickness and type of the desired metal-containing film. The reaction temperature may be a temperature at which the source for forming the metal-containing film can react sufficiently. In one embodiment, the reaction temperature may be in the range of room temperature to about 500 ℃, e.g., about 150 ℃ to about 400 ℃.

When the process of forming the metal-containing film according to process P20 of fig. 1 is performed using an ALD process, the film thickness of the metal-containing film may be controlled by adjusting the number of cycles of the ALD process. Forming a metal-containing film on a substrate using an ALD process may include: a source gas introduction process in which a vapor formed by evaporating a source for forming a metal-containing film containing an organometallic addition compound according to an embodiment is introduced into a deposition reactor; a precursor film forming process in which a precursor film is formed on a surface of a substrate by using vapor; a discharge process in which unreacted source gas remaining on the substrate is discharged from the reaction space; and a process in which the precursor thin film is chemically reacted with a reactive gas to form a metal-containing film on a surface of the substrate.

In one embodiment, the process of vaporizing the source for forming the metal-containing film may be performed in a source vessel or vaporizer. The process of evaporating the source for forming the metal-containing film may be performed at a temperature of about 0 ℃ to about 200 ℃. When evaporating the source for forming the metal-containing film, the internal pressure of the source container or the evaporator may be in the range of about 1 pa to about 10,000 pa.

Fig. 2 is a detailed flowchart of a method of forming a metal-containing film by using the method of manufacturing an IC device according to an exemplary embodiment. A method of forming a metal-containing film by using an ALD process according to process P20 of fig. 1 will be described with reference to fig. 2.

Referring to fig. 2, in process P21, a source gas containing an organometallic addition compound having a structure of general formula (I) may be evaporated.

In one embodiment, the source gas may comprise the sources described above for forming metal-containing films. The process of evaporating the source gas can be performed at a temperature of about 0 ℃ to about 200 ℃. When evaporating the source gas, the internal pressure of the source container or evaporator may be in the range of about 1 Pa to about 10,000 Pa.

In process P22, the source gas evaporated according to process P21 may be supplied onto the substrate, and thus, a metal source adsorption layer containing niobium atoms, tantalum atoms, or vanadium atoms may be formed on the substrate. In this case, the reaction temperature may be in the range of room temperature to about 500 ℃, for example, about 150 ℃ to about 400 ℃. The reaction pressure may be in the range of from about 1 pa to about 10,000 pa, for example from about 10 pa to about 1,000 pa.

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

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

In one embodiment, an inert gas such as argon (Ar), helium (He), or neon (Ne), or nitrogen may be usedQi (N)₂) As a purge gas.

In one embodiment, instead of the purge gas, the reaction space may be exhausted by reducing the pressure of the reaction space in which the substrate is loaded. In this case, the reaction space may be maintained at a pressure of about 0.01 Pa to about 300 Pa, for example about 0.01 Pa to about 100 Pa, in order to reduce the pressure in the reaction chamber.

In one embodiment, a process of heating the substrate on which the metal source adsorption layer containing niobium atoms, tantalum atoms, or vanadium atoms is formed, or a process of annealing the reaction chamber containing the substrate may also be performed. The annealing process may be performed at a temperature of from room temperature to about 500 ℃, for example at a temperature of from about 50 ℃ to about 400 ℃.

In process P24, a reactive gas may be supplied onto the metal source adsorption layer formed on the substrate, whereby a metal-containing film may be formed on an atomic level.

In one embodiment, when a metal oxide film containing niobium atoms, tantalum atoms, or vanadium atoms is formed on a substrate, the reactive gas may be an oxidizing gas, for example, O₂、O₃、O₂Plasma, H₂O、NO₂、NO、N₂O、CO、CO₂、H₂O₂、HCOOH、CH₃COOH、(CH₃CO)₂O, alcohol, peroxide, sulfur oxide, or combinations thereof.

In one embodiment, when forming a metal nitride film containing niobium atoms, tantalum atoms, or vanadium atoms on a substrate, the reactive gas may include: for example, NH₃、N₂Plasma, mono-alkyl amines, di-alkyl amines, tri-alkyl amines, organic amine compounds, hydrazine compounds, and combinations thereof.

In one embodiment, the reactive gas may be a reducing gas, e.g., H₂。

In process P24, the reaction space may be maintained at a temperature of room temperature to about 500 ℃, for example, at a temperature of about 50 ℃ to about 400 ℃ or at a temperature of about 50 ℃ to about 200 ℃, so that the metal source adsorption layer containing niobium atoms, tantalum atoms, or vanadium atoms may sufficiently react with the reactive gas. In process P24, the pressure in the reaction space may be in the range of from about 1 pa to about 10,000 pa, for example from about 10 pa to about 1,000 pa.

In process P24, the reactive gas may be treated with a plasma. During the plasma processing process, the Radio Frequency (RF) output may be in a range of about 0W to about 1,500W, such as about 50W to about 600W.

In process P25, unwanted byproducts remaining on the substrate may be removed by supplying a purge gas onto the substrate.

In one embodiment, an inert gas such as argon (Ar), helium (He), or neon (Ne), or nitrogen (N) may be used₂) As a purge gas.

In process P26, processes P21 through P25 of fig. 2 may be repeated until the metal-containing film is formed to a desired thickness.

A thin film deposition process including a series of processes, such as processes P21 through P25, may be defined as a cycle, and the cycle may be repeated a plurality of times until the metal-containing film is formed to a desired thickness. In one embodiment, after the cycle is performed once, the unreacted gas may be discharged from the reaction chamber by performing a discharge process using a purge gas similar to the process P23 or P25, and then a subsequent cycle may be performed.

In one embodiment, the conditions for supplying the source (e.g., the evaporation temperature or evaporation pressure of the source), the reaction temperature, and the reaction pressure may be adjusted 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 be degraded. If the deposition rate of the metal-containing film is too low, the productivity is lowered. In one embodiment, the deposition rate of the metal-containing film can be in a range from about 0.01nm/min to about 100nm/min, such as from about 1nm/min to about 50 nm/min.

The method of forming the metal-containing film described with reference to fig. 2 is only one example, and various modifications and changes of the method may be made.

In one embodiment, in order to form a metal-containing film on a substrate, at least one of other precursors, a reactive gas, a carrier gas, and a purge gas may be supplied to the substrate simultaneously or sequentially with the organometallic addition compound represented by the general formula (I). The details of the other precursors, reactive gases, carrier gases and purge gases that may be supplied to the substrate with the organometallic addition compound represented by formula (I) are as described above.

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

Fig. 3A to 3D are schematic diagrams of configurations of deposition systems 200A, 200B, 200C, and 200D that may be used to form metal-containing films in methods of fabricating IC devices according to example embodiments.

Each of the deposition systems 200A, 200B, 200C, and 200D shown in fig. 3A to 3D may include: a fluid delivery unit 210; a thin film forming unit 250 configured to perform a deposition process of forming a thin film on the substrate W by using the process gas supplied from the source container 212 included in the fluid delivery unit 210; and an exhaust system 270 configured to exhaust gas or byproducts that may remain after the reaction in the thin film forming unit 250.

The thin film forming unit 250 may include a reaction chamber 254, the reaction chamber 254 including a susceptor 252 configured to support a substrate W. A shower head 256 may be installed at the top end unit inside the reaction chamber 254. The showerhead 256 may be configured to supply gas supplied by the fluid delivery unit 210 onto the substrate W.

The fluid delivery unit 210 may include: an inlet line 222 configured to supply a carrier gas from the outside to the source container 212, and an outlet line 224 configured to supply the source compound contained in the source container 212 to the thin film forming unit 250. A valve V1 and a Mass Flow Controller (MFC) M1 may be installed at the inlet line 222, and a valve V2 and an MFC M2 may be installed at the outlet line 224. The inlet line 222 and the outlet line 224 may be connected to each other by a bypass line 226. A valve V3 may be installed at the bypass line 226. Valve V3 may be operated by pneumatic pressure using an electric motor or other remote control unit.

The source compound supplied from the source container 212 may be supplied into the reaction chamber 254 through the inlet line 266 of the membrane forming unit 250 connected to the outlet line 224 of the fluid transfer unit 210. The source compound supplied from the source container 212 may be supplied into the reaction chamber 254 together with a carrier gas supplied through the inlet line 268, if necessary. A valve V4 and MFC M3 may be installed at the inlet line 268 into which the carrier gas is supplied.

The thin film forming unit 250 may include: an inlet line 262 configured to supply purge gas into the reaction chamber 254, and an inlet line 264 configured to supply reactive gas. A valve V5 and MFC M4 may be installed at inlet line 262, and a valve V6 and MFC M5 may be installed at inlet line 264.

The process gas used in the reaction chamber 254 and the reaction by-products to be discarded 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 at the exhaust line 272. The vacuum pump 274 can eliminate the process gases and reaction byproducts exhausted from the reaction chamber 254.

A trap 276 may be installed in the exhaust line 272 on the upstream side of the vacuum pump 274. The trap 276 may trap reaction byproducts generated, for example, from the unreacted process gas in the reaction chamber 254, and prevent the reaction byproducts from flowing into the vacuum pump 274 disposed at the downstream side.

The trap 276 installed at the exhaust line 272 may trap reaction byproducts that may be generated due to a reaction between process gases, for example, and may prevent the reaction byproducts from flowing to the downstream side of the trap 276. The trap 276 may be configured to be cooled by a chiller or water cooling device.

In addition, a bypass line 278 and an Automatic Pressure Controller (APC)280 may be installed in the discharge line 272 on the upstream side of the trap 276. Valve V7 may be installed at bypass line 278, and valve V8 may be installed at a portion where discharge line 272 may extend parallel to bypass line 278.

As in the deposition systems 200A and 200C shown in fig. 3A and 3C, a heater 214 may be installed in the source container 212. The source compound contained in the source container 212 may be maintained at a high temperature by the heater 214.

As in the deposition systems 200B and 200D shown in fig. 3B and 3D, an evaporator 258 may be installed at an inlet line 266 of the thin film forming unit 250. The evaporator 258 can evaporate the fluid supplied in a liquid state by the fluid delivery unit 210 and supply the evaporated source compound into the reaction chamber 254. The source compound vaporized by vaporizer 258 may be supplied into reaction chamber 254 along with a carrier gas supplied through inlet line 268. The supply of source compound to the reaction chamber 254 through the vaporizer 258 can be controlled by a valve V9.

In one embodiment, as in the deposition systems 200C and 200D shown in fig. 3C and 3D, the thin film forming unit 250 may include a Radio Frequency (RF) power supply 292 and an RF matching system 294 connected to the reaction chamber 254 in order to generate plasma in the reaction chamber 254.

In one embodiment, as shown in fig. 3A through 3D, the deposition systems 200A, 200B, 200C, and 200D may be configured such that one source vessel 212 is connected to the reaction chamber 254. In one embodiment, a plurality of source containers 212 may be provided in the fluid delivery unit 210, and each of the plurality of source containers 212 may be connected to the reaction chamber 254. The number of source containers 212 connected to the reaction chamber 254 may be a suitable number.

In one embodiment, the source for forming a metal-containing film comprising the organometallic addition compound of formula (I) can be evaporated by using the evaporator 258 in either of the deposition systems 200B and 200D shown in FIGS. 3B and 3D.

In the method of manufacturing an IC device described with reference to fig. 1 and 2, a metal-containing film may be formed on a substrate W using any one of the deposition systems 200A, 200B, 200C, and 200D shown in fig. 3A to 3D. In order to form a metal-containing film on the substrate W, the organometallic addition compound of the general formula (I) according to the embodiment may be delivered by using various methods and supplied into a reaction space of a thin film forming system, for example, into the reaction chamber 254 of each of the deposition systems 200A, 200B, 200C, and 200D shown in fig. 3A to 3D.

In one 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 systems 200A, 200B, 200C, and 200D shown in fig. 3A to 3D.

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

The reaction temperature may be a temperature at which the organometallic addition compound according to the embodiment, for example, the organometallic addition compound of the general formula (I), can sufficiently react. In one embodiment, the reaction temperature may be a temperature above about 150 ℃. In one embodiment, the reaction temperature may be selected in the range of about 150 ℃ to about 400 ℃ or in the range of about 200 ℃ to about 350 ℃.

In one embodiment, 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 a photo CVD process, and in the range of about 10 pa to about 2,000 pa in the case of a plasma CVD process.

The deposition rate can be controlled by adjusting conditions (e.g., evaporation temperature and evaporation pressure), reaction temperature, and reaction pressure for supplying the source compound. In one embodiment, in a method of fabricating an IC device according to an embodiment, a deposition rate of the metal-containing film may be selected in a range of about 0.01nm/min to about 100nm/min, for example, in a range of about 1nm/min to about 50 nm/min. When the metal-containing film is formed by using the ALD process, the number of cycles of the ALD process may be adjusted to control the thickness of the metal-containing film.

In one embodiment, energy (e.g., plasma, light, or voltage) may be applied when the metal-containing film is formed using an ALD process. The time period for which the energy is applied may be chosen differently. In one embodiment, energy (e.g., plasma, light, or voltage) may be applied when a source gas comprising an organometallic addition compound is introduced into the reaction chamber, when the source gas is adsorbed on the substrate W, when a purge gas is used for the exhaust process, when a reactive gas is introduced into the reaction chamber, or between periods when the above processes are performed.

In one embodiment, after the metal-containing film is formed using the organometallic addition compound of the general formula (I), a process of annealing the metal-containing film under an inert atmosphere, an oxidizing atmosphere, or a reducing atmosphere may also be performed. In one embodiment, the metal-containing film may be subjected to a reflow process in order to remove roughness from the surface of the metal-containing film. Each of the annealing process and the reflow process may be performed under a temperature condition of about 200 ℃ to about 1,000 ℃, for example, about 250 ℃ to about 500 ℃.

In one embodiment, various types of metal-containing films may be formed by appropriately selecting the organometallic addition compound according to the embodiment, other precursors that can be used together with the organometallic addition compound, reactive gases, and conditions for forming a thin film. In one embodiment, the metal-containing film formed using the method according to the embodiment may include niobium atoms, tantalum atoms, or vanadium atoms. In one embodiment, the metal-containing film may include a niobium film, a niobium oxide film, a niobium nitride film, a niobium alloy film, a niobium-containing composite oxide film, a tantalum oxide film, a tantalum nitride film, a tantalum alloy film, or a tantalum-containing composite oxide film. The niobium alloy film may comprise, for example, an Nb-Hf alloy or an Nb-Ti alloy. The tantalum alloy film may comprise, for example, a Ta-Ti alloy or a Ta-W alloy. The metal-containing film formed using the method according to the embodiment may be used as a material for respective components included in an IC device. In one embodiment, the metal-containing film may be used for an electrode material of a Dynamic Random Access Memory (DRAM) device, a gate of a transistor, a resistor, a diamagnetic film for a recording layer of a hard device, a catalyst material for a solid polymer fuel cell, a conductive barrier film for a metal wire, a dielectric film of a capacitor, a barrier metal film for a liquid crystal, a component for a thin-film solar cell, a component for a semiconductor device, a nanostructure, or the like.

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

Referring to fig. 4A, an interlayer dielectric 320 may be formed on a substrate 310 including a plurality of active regions AC. Thereafter, a plurality of conductive regions 324 may be formed through the interlayer dielectric 320 and AC-connected to the plurality of active regions.

The substrate 310 may include a semiconductor such as silicon (Si) or germanium (Ge), or a compound semiconductor such as silicon germanium (SiGe), silicon carbide (SiC), gallium arsenide (GaAs), indium arsenide (InAs), or indium phosphide (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. The device isolation region 312 may include a silicon oxide film, a silicon nitride film, a silicon oxynitride film, or a combination thereof. The interlayer dielectric 320 may include a silicon oxide film. A plurality of conductive regions 324 may be connected to one terminal of a switching device (e.g., a field effect transistor) formed on the substrate 310. The plurality of conductive regions 324 may comprise polysilicon, metal, conductive metal nitride, metal silicide, or combinations thereof.

Referring to fig. 4B, an insulating layer 328 may be formed covering the interlayer dielectric 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 etch selectivity with respect to the interlayer dielectric 320 and a molding film 330 (see fig. 4C) formed in a subsequent process. Insulating layer 328 may comprise silicon nitride, silicon oxynitride, or a combination thereof.

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

The molding film 330 may include an oxide film. In one embodiment, the molding film 330 may include an oxide film, such as borophosphosilicate glass (BPSG), phosphosilicate glass (PSG), or Undoped Silicate Glass (USG). To form the molding film 130, a thermal CVD process or a plasma CVD process may be used. The thickness of the molded membrane 330 may be, for example, aboutTo about In one embodiment, the molded membrane 330 may include a support membrane. The support film may comprise a material having an etch selectivity with respect to the molding film 330. The support film may contain an etching atmosphere relative to when the molding film 330 is removed in a subsequent process, for example, relative to an etching atmosphere containing ammonium fluoride (NH)₄F) Hydrofluoric acid (HF) and water etchants have materials with lower etch rates. In one embodiment, the support film may comprise silicon nitride, silicon carbonitride, tantalum oxide, titanium oxide, or combinations thereof.

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

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. A region 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 film 342 and the mold film 330 may be dry-etched using the mask pattern 344 as an etch mask and the insulating layer 328 as an etch stop layer, thereby forming sacrificial patterns 342P and mold patterns 330P defining a plurality of holes H1. In one embodiment, the insulating layer 328 may also be etched due to the over-etching, and thus an insulating pattern 328P exposing the plurality of conductive regions 324 may be formed.

Referring to fig. 4F, the mask pattern 344 may be removed from the resultant of fig. 4E, and then a conductive film 350 for forming a lower electrode, which fills the plurality of holes H1 and covers the exposed surface of the sacrificial pattern 342P, is formed.

The conductive film 350 for forming the lower electrode may include a doped semiconductor, a conductive metal nitride, a metal silicide, a conductive oxide, or a combination thereof. In one embodiment, the conductive film 350 for forming the lower electrode may include: for example, NbN, TiN, TiAlN, TaN, TaAlN, W, WN, Ru, RuO₂、SrRuO₃、Ir、IrO₂、Pt、PtO、SRO(SrRuO₃)、BSRO((Ba,Sr)RuO₃)、CRO(CaRuO₃)、LSCo((La,Sr)CoO₃) Or a combination thereof. To form the conductive film 350 for forming the lower electrode, CVD, metal organic CVD (mocvd), or ALD process may be used.

In one embodiment, in order to form the conductive film 350 for forming the lower electrode, a metal-containing film may be formed using the process P20 of fig. 1 or the method described with reference to fig. 2. In one embodiment, the conductive film 350 for forming the lower electrode may include a multilayer structure including a TiN film and a NbN film. The NbN film may be a film formed using process P20 of fig. 1 or the method described with reference to fig. 2. The conductive film 350 for forming the lower electrode may be formed using any one of the deposition systems 200A, 200B, and 200C and 200D shown in fig. 3A to 3D.

Referring to fig. 4G, an upper side of the conductive film 350 for forming the lower electrode may be partially removed, thereby dividing the conductive film 350 for forming the lower electrode into a plurality of lower electrodes LE.

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

Referring to fig. 4H, the outer surfaces of the plurality of lower electrodes LE may be exposed by removing the mold pattern 330P from the resultant of fig. 4G. By using an etchant containing ammonium fluoride (NH)₄F) Hydrofluoric acid (HF), and water) to remove the mold pattern 330P.

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

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

In one embodiment, the dielectric film 360 may include 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. Can be produced by an ALD processA dielectric film 360 is formed. In one embodiment, to form at least a portion of the dielectric film 360, a metal-containing film may be formed using process P20 of fig. 1 or the method described with reference to fig. 2. In one embodiment, dielectric film 360 may include a tantalum oxide film, which may be a film formed using process P20 of fig. 1 or the method described with reference to fig. 2. The dielectric film 360 may be formed using any one of the deposition systems 200A, 200B, 200C, and 200D shown in fig. 3A to 3D. The dielectric film 360 may have a thickness of aboutTo aboutIs measured.

In one embodiment, before forming the dielectric film 360 on the plurality of lower electrodes LE as described with reference to fig. 4I, a process of forming a lower interface film to cover a surface of each of the plurality of lower electrodes LE may also be performed. In this case, the dielectric film 360 may be formed on the lower interface film. The lower interface film may include a metal-containing film comprising niobium, tantalum, or vanadium. The metal-containing film included in the lower interface film may be formed using the process P20 of fig. 1 or the method described with reference to fig. 2. Any of the deposition systems 200A, 200B, 200C, and 200D shown in fig. 3A through 3D may be used to form the lower interface film.

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 one embodiment, the upper electrode UE may include: NbN, TiN, TiAlN, TaN, TaAlN, W, WN, Ru, RuO₂、SrRuO₃、Ir、IrO₂、Pt、PtO、SRO(SrRuO₃)、BSRO(Ba,Sr)RuO₃)、CRO(CaRuO₃)、LSCo((La,Sr)CoO₃) Or a combination thereof. The upper electrode UE may be formed using a CVD process, an MOCVD process, a Physical Vapor Deposition (PVD) process, or an ALD process.

In one embodiment, to form the upper electrode UE, the metal-containing film may be formed using the process P20 of fig. 1 or the method described with reference to fig. 2. The upper electrode UE may be formed using any one of the deposition systems 200A, 200B, 200C, and 200D shown in fig. 3A to 3D.

In one embodiment, before forming the upper electrode UE on the dielectric film 360 as described with reference to fig. 4J, a process of forming an upper interface film to cover the surface of the dielectric film 360 may also be performed. In this case, the upper electrode UE may be formed on the upper interface film. The upper interface film may include a metal-containing film comprising niobium, tantalum, or vanadium. The metal-containing film included in the upper interface film may be formed using process P20 of fig. 1 or the method described with reference to fig. 2. Any one of the deposition systems 200A, 200B, 200C, and 200D shown in fig. 3A to 3D may be used to form the upper interface film.

In one embodiment, in the method of manufacturing the IC device 300, as shown in fig. 4A to 4J, each of the plurality of lower electrodes LE may have a cylindrical shape. In one embodiment, each of the plurality of lower electrodes LE may have a cup-shaped sectional structure whose bottom is blocked or a cylindrical sectional structure.

In the IC device 300 manufactured by using the method described with reference to fig. 4A to 4J, the capacitor 370 may include the lower electrode LE having a 3D electrode structure. In order to compensate for the reduction in capacitance due to the reduction in design rule, the aspect ratio of the lower electrode LE having the 3D structure is increased, and the dielectric film 360 having good quality can be formed in a deep, narrow 3D space using the ALD process. In the method of manufacturing the IC device 300 according to the embodiment described with reference to fig. 4A to 4J, the lower electrode LE, the dielectric film 360, or the upper electrode UE may be formed using the organometallic addition compound of the general formula (I) according to the embodiment, whereby process stability may be improved.

The following examples and comparative examples are provided to highlight the nature of one or more embodiments, but it will be understood that these examples and comparative examples are not to be construed as limiting the scope of the embodiments, nor are the comparative examples to be construed as being outside of the scope of the embodiments. In addition, it will be understood that the embodiments are not limited to the specific details described in the examples and comparative examples.

Synthesis example 1

Synthesis of Compound of formula 2

9.40g (50.0mmol) of niobium pentafluoride and 250mL of anhydrous dichloromethane were placed in a 500-mL 4-necked flask under an argon (Ar) atmosphere, and the resultant liquid was stirred while keeping the temperature of the resultant liquid at about 25 ℃. Thereafter, 17.7g (51.5mmol) of tris (2,2, 2-trifluoroethyl) phosphate were added dropwise at ambient temperature and stirred for about 5 hours. The solvent and unreacted tris (2,2, 2-trifluoroethyl) phosphate were distilled under reduced pressure, followed by purification by distillation, to obtain 10.2g of the objective product (yield 38.2%).

(analysis value)

(1)1H-NMR (heavy benzene)

3.70ppm (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 Compound of formula 6

13.5g (50.0mmol) of niobium pentachloride and 300mL of anhydrous dichloromethane were placed in a 500-mL 4-necked flask under an argon atmosphere, and the resulting liquid was stirred while maintaining the temperature of the resulting liquid at about 25 ℃. Thereafter, 17.7g (51.5mmol) of tris (2,2, 2-trifluoroethyl) phosphate were added dropwise at ambient temperature and stirred for about 5 hours. The solvent and unreacted tris (2,2, 2-trifluoroethyl) phosphate were distilled under reduced pressure and then subjected to purification by distillation to obtain 28.0g of the objective product (yield 91.2%).

(analysis value)

(1)1H-NMR (heavy benzene)

3.87ppm (6H, double four peaks)

(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 Compound of formula 7

13.5g (50.0mmol) of niobium pentachloride and 300mL of anhydrous dichloromethane were placed in a 500-mL 4-necked flask under an argon atmosphere, and the resulting liquid was stirred while maintaining the temperature of the resulting liquid at about 25 ℃. Thereafter, 28.2g (51.5mmol) of tris (1,1,1,3,3, 3-hexafluoro-2-propyl) phosphate were added dropwise at ambient temperature and stirred for about 5 hours. The solvent and unreacted tris (1,1,1,3,3, 3-hexafluoro-2-propyl) phosphate were distilled under reduced pressure, followed by distillation purification to obtain 20.5g of the objective product (yield 50.2%).

(analysis value)

(1)1H-NMR (heavy benzene)

4.81ppm (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

17.9g (50.0mmol) of TaCl were introduced under argon₅And 300mL of anhydrous dichloromethane were placed in a 500-mL 4-necked flask, and the resultant liquid was stirred while maintaining the temperature of the resultant liquid at about 25 ℃. Thereafter, 17.7g (51.5mmol) of tris (2,2, 2-trifluoroethyl) phosphate were added dropwise at ambient temperature and stirred for about 5 hours. The solvent and unreacted tris (2,2, 2-trifluoroethyl) phosphate were distilled under reduced pressure and then subjected to purification by distillation to obtain 30.9g of the objective product (yield 87.9%).

(analysis value)

(1)1H-NMR (heavy benzene)

3.85ppm (6H, double four peaks)

(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％)

Examples 1 to 4 and comparative examples 1 to 4

Next, the thermogravimetric-differential thermal analysis (TG-DTA) 50% mass reduction temperature T1 (at normal pressure), phase (at 25 ℃) and melting point of the compounds of formulae 2,6, 7 and 14 obtained in synthesis examples 1 to 4 and each of the following comparative compounds 1 to 4 were measured as follows.

"nBu" refers to n-butyl.

(1) TG-DTA at atmospheric pressure

The 50% mass reduction temperature T1 of each of the compounds of formulae 2,6, 7, and 14 obtained in synthesis examples 1 to 4 and comparative compounds 1 to 4 was measured using the TG-DTA technique under the conditions of normal pressure, Ar flow of 100mL/min, temperature rise rate of 10 ℃/min, and sweep temperature range of about 30 ℃ to about 600 ℃, and the measurement results thereof are shown in table 1.

(2) Melting Point of the Compound

The results obtained by visually observing the phases of the compounds of formulae 2,6, 7 and 14 obtained in synthesis examples 1 to 4 and comparative compounds 1 to 4 at a temperature of about 25 ℃ are shown in table 1. Table 1 also shows the results obtained by measuring the melting point of a compound that is solid at a temperature of about 25 ℃.

[ Table 1]

According to the results of table 1, the 50% mass reduction temperature T1 of each of the compounds of formulae 2,6, 7, and 14 measured at normal pressure using the TG-DTA technique was about 215 ℃ or less, and thus, the compounds of formulae 2,6, 7, and 14 had higher vapor pressures. In addition, all of the compounds of formulas 2,6, 7 and 14 are liquid at a temperature of about 25 ℃ and have a melting point below about 25 ℃.

In contrast, each of comparative compounds 1 to 4 had a higher melting point of about 115 ℃ or higher. The 50% mass reduction temperature T1 of each of comparative compounds 1 and 3 measured using the TG-DTA technique at normal pressure is about 180 ℃, and therefore comparative compounds 1 and 3 are compounds having a higher vapor pressure similar to the compounds according to the embodiments. However, comparative compounds 1 and 3 have very high melting points above about 205 ℃.

Examples 5 to 8 and comparative examples 5 to 8 (formation of Metal-containing film)

Next, a niobium nitride film or a tantalum nitride film was formed on the silicon substrate using each of the compounds of formulae 2,6, 7, and 14 obtained in synthesis examples 1 to 4 and comparative compounds 1 to 4 as a source and using the deposition system of fig. 3A. The conditions of the ALD process for forming the niobium nitride film or the tantalum nitride film are as follows.

< Condition >

Reaction temperature (substrate temperature): 250 deg.C

Reactive gas (b): ammonia gas

< procedure >

One cycle including a series of processes (1) to (4) described below was repeated 150 times under the above conditions.

Process (1): a vapor is generated by an evaporation source under the conditions that a source container is heated to a temperature of about 90 ℃ and maintained at an internal pressure of about 100 pa, the vapor is introduced into a chamber, and a niobium nitride film or a tantalum nitride film is deposited for about 30 seconds in the chamber maintained at a pressure of about 100 pa.

Process (2): an argon (Ar) purge process was performed for about 10 seconds to remove unreacted source from the chamber.

Process (3): supplying the reactive gas into the chamber at a pressure of about 100 pa causes the reaction to take place for about 30 seconds.

Process (4): an argon purge process was performed for about 10 seconds to remove unreacted source from the chamber.

The thickness of each of the thin films obtained in the processes (1) to (4) was measured using an X-ray reflectance technique, and the compound of each of the obtained thin films was confirmed using an X-ray diffraction technique. The carbon content of each of the resulting thin films was measured using an X-ray photoelectron spectroscopy (XPS) technique, and the measurement results thereof are shown in table 2.

[ Table 2]

As can be seen from the results of table 2, in the thin films obtained using the ALD process, the carbon content of each of the thin films obtained using comparative compounds 2 and 4 was 6 atomic percent (atomic%) or more. In contrast, each of the thin films obtained using the compounds of formulae 2,6, 7 and 14 has a carbon content of about 0.1 atomic% (which is a detection limit) or less. Therefore, the films obtained using the compounds of formulae 2,6, 7 and 14 are films having good quality. In addition, as a result of evaluating the thickness of the thin films obtained after 150 cycles of the ALD process, each of the thin films obtained using the comparative compounds 1,2, 3, and 4 was about 3nm or less, and each of the thin films obtained using the compounds of formulae 2,6, 7, and 14 was about 5.0nm or more. From this, it can be seen that the productivity of the film forming process is excellent.

As can be seen from the examples, the organometallic addition compounds according to examples 1 to 8 have a low melting point, a high vapor pressure, and contribute to improving the productivity of the thin film forming process when the organometallic addition compounds are used as a source in an ALD process or a CVD process for forming a thin film.

As a summary and review, the source compound for forming the metal-containing film should provide excellent void filling characteristics and step coverage characteristics during the formation of the metal-containing film for manufacturing IC devices, and is advantageous in terms of process stability and mass-producibility due to its easy handleability.

One or more embodiments may provide organometallic addition compounds that include niobium, tantalum, or vanadium as the metal.

One or more embodiments may provide an organometallic addition compound that may be used as a source compound capable of providing excellent thermal stability, process stability, and mass-producibility during the formation of a metal-containing film used to fabricate an Integrated Circuit (IC) device.

One or more embodiments may provide a method of manufacturing an IC device, by which a metal-containing film having good quality may be formed using a metal-containing source compound capable of providing excellent process stability and mass-producibility, thereby providing desired electrical properties.

Example embodiments have been 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, characteristics and/or elements described with respect to a particular embodiment may be used alone or in combination with features, characteristics and/or elements described with respect to other embodiments, as will be apparent to one of ordinary skill in the art at the time of filing the present application, unless explicitly stated otherwise. Accordingly, it will 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.