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

Abstract

Disclosed are an organometallic addition compound and a method for manufacturing an integrated circuit (IC) device. The organometallic addition compound is represented by the general formula (I): 1 、R 2 and R 3 are each independently C1 to C5 alkyl, R 1 、R 2 and R 3 At least one of them is a C1 to C5 alkyl group in which at least one hydrogen atom is substituted by 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.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] Korean Patent Application No. 10-2020-0032285 filed on March 16, 2020, in the Korean Intellectual Property Office and Korean Patent Application No. 10-2020-0098822 filed on August 6, 2020, in the Korean Intellectual Property Office are incorporated herein by reference in their entirety, both of which are entitled “Organometallic addition compounds and methods for manufacturing integrated circuits using the same.” Technical Field

[0003] Embodiments relate to organometallic addition compounds and methods of fabricating integrated circuit (IC) devices using the organometallic addition compounds. Background Art

[0004] In recent years, due to the development of electronic technology, the size reduction of semiconductor devices has been rapidly progressing, and thus patterns included in electronic devices have been miniaturized. Summary of the Invention

[0005] The embodiment can be achieved by providing an organometallic addition compound represented by the general formula (I):

[0006] General formula (I)

[0007]

[0008] Wherein, in the general formula (I), R 1 、R 2 and R 3 are each independently C1 to C5 alkyl, R 1 、R 2 and R 3 At least one of them is a C1 to C5 alkyl group in which at least one hydrogen atom is substituted by 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.

[0009] The embodiment can be achieved 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 the general formula (I),

[0010] General formula (I)

[0011]

[0012] Wherein, in the general formula (I), R 1 、R 2 and R 3 are each independently C1 to C5 alkyl, R1 、R 2 and R 3 At least one of them is a C1 to C5 alkyl group in which at least one hydrogen atom is substituted by 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. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Features of the present application will become apparent to those skilled in the art by describing in detail exemplary embodiments with reference to the accompanying drawings, in which:

[0014] Figure 1 is a flow chart of a method of manufacturing an integrated circuit (IC) device according to an embodiment;

[0015] Figure 2 is a detailed flow chart of a method of forming a metal-containing film by using a method of manufacturing an IC device according to an exemplary embodiment;

[0016] Figures 3A to 3D is a schematic diagram of a configuration of a deposition system that may be used to form a metal-containing film in a method of manufacturing an IC device according to an exemplary embodiment; and

[0017] Figures 4A to 4J are cross-sectional views of stages in a method of fabricating an IC device according to an embodiment. DETAILED DESCRIPTION

[0018] When the term "substrate" is used herein, it should be understood as the substrate itself, or a stacked structure including a substrate and a predetermined layer or film formed on the surface of the substrate. When the term "surface of a substrate" is used herein, it should be understood as the exposed surface of the substrate itself, or the outer surface of a predetermined layer or film formed on the substrate. As used herein, the term "room temperature" or "ambient temperature" refers to a temperature in the range of about 20°C to about 28°C, and may vary according to the season.

[0019] The organometallic addition compound according to the embodiment may have a structure in which an organic phosphate group is bonded to a coordinating 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).

[0020] General formula (I)

[0021]

[0022] In general formula 1, R 1 、R 2 and R 3Can be or include, for example, C1 to C5 alkyl (for example, substituted or unsubstituted C1 to C5 alkyl). In one embodiment, R 1 、R 2 and R 3 At least one of the may 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 (e.g., a niobium atom, a tantalum atom, or a vanadium atom), X may be a halogen atom, m may be an integer from 3 to 5, and n may be 1 or 2. As used herein, the term "or" is not an exclusive term, for example, "A or B" will include A, B, or A and B.

[0023] In one embodiment, R 1 、R 2 and R 3 At least one of may be a straight chain alkyl group (e.g., a straight chain C1 to C5 alkyl group). 1 、R 2 and R 3 At least one of the groups may be a branched alkyl group (eg, a branched C3 to C5 alkyl group).

[0024] In one embodiment, R 1 、R 2 and R 3 Each independently may 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.

[0025] In one embodiment, R 1 、R 2 and R 3 Each independently may be or include, for example, a trifluoromethyl group, a trifluoroethyl group, a hexafluoroisopropyl group or a nonafluoro-tert-butyl group.

[0026] 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 increased.

[0027] The organometallic addition compound according to the embodiment may be liquid at room temperature. When the organometallic addition compound is liquid at room temperature, the organometallic addition compound may be easily handled. In the general formula (I), when R 1 、R 2 and R 3When at least one of the is a branched alkyl group, the organometallic addition compound can be advantageously placed in a liquid phase or in a liquid phase at room temperature. In one embodiment, the organometallic addition compound can be a liquid at room temperature under atmospheric pressure (e.g., 1 atm) or under pressure conditions that ensure that the compound is in a liquid phase.

[0028] 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.

[0029] In one embodiment, in Formula (I), m may be 5, and n may be 1.

[0030] 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 R 1 、R 2 and R 3 Each may independently be a branched alkyl group.

[0031] 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 R 1 、R 2 and R 3 Each may independently be a branched alkyl group.

[0032] 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 R 1 、R 2 and R 3 Each may independently be an alkyl group in which all hydrogen atoms are substituted with fluorine atoms (eg, a C1 to C5 perfluoroalkyl group).

[0033] 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 R 1 、R 2 and R 3 Each may independently be an alkyl group in which all hydrogen atoms are substituted with fluorine atoms.

[0034] The organometallic addition compound according to one embodiment may have a structure in which an organic phosphate group is bonded to a coordinated metal compound in the form of an adduct. The organometallic addition compound can be used as a metal precursor during the formation of a metal-containing film using a chemical vapor deposition (CVD) process or an atomic layer deposition (ALD) process. In this case, when the organometallic addition compound is stored in a container, the organophosphate group can protect the coordinated metal compound through a coordination bond. In addition, when the organometallic addition compound is transported to a deposition reaction chamber for forming a metal-containing film, the organometallic addition compound can 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.

[0035] In one embodiment, the organometallic addition compound may be represented by one of the following Formulae 1 to 16.

[0036]

[0037] The organometallic addition compound can be prepared by utilizing a suitable reaction. For example, niobium pentachloride can be reacted with a phosphate having a structure corresponding to the final structure to be synthesized in a dichloromethane solvent at a temperature of approximately 25°C to obtain a solution, from which the solvent and unreacted products can be distilled. Subsequently, the organometallic addition compound according to the embodiment can be synthesized by using a distillation and purification method.

[0038] The organometallic addition compound according to the embodiment may be appropriately used as a source for a CVD process or an ALD process.

[0039] Figure 1 is a flowchart of a method of manufacturing an integrated circuit (IC) device according to an embodiment.

[0040] Reference Figure 1 , in process P10, a substrate may be prepared.

[0041] The substrate may include silicon, ceramic, glass, metal, metal nitride or a combination thereof. The ceramic may include silicon nitride, titanium nitride, tantalum nitride, titanium oxide, niobium oxide, zirconium oxide, hafnium oxide, lanthanum oxide or a combination thereof. Each of the metal and 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 groove structure.

[0042] In one embodiment, the substrate may have a Figure 4A The substrate 310 is constructed in the same manner as described.

[0043] exist Figure 1 In process P20, a metal-containing film may be formed on a substrate using a source for forming a metal-containing film. In one embodiment, the source may include an organometallic addition compound represented by formula (I).

[0044] The source for forming the metal-containing film may include the organometallic addition compound according to the 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 liquid at room temperature.

[0045] The source for forming the metal-containing film can be changed, for example, it can be selected according to the film to be formed. In one embodiment, the metal-containing film 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 the 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 only include the organometallic addition compound according to the embodiment, and may not include other metal compounds and semi-metallic compounds.

[0046] In one embodiment, the metal-containing film to be formed may further contain other metals in addition to niobium, tantalum, or vanadium. In one embodiment, when the metal-containing film to be formed is a film containing other metals or semimetals in addition to niobium, tantalum, or vanadium, in addition to the organometallic addition compound according to the embodiment, 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 one embodiment, in addition to the organometallic addition compound according to the embodiment, the source for forming the metal-containing film may further contain an organic solvent or a nucleophilic agent.

[0047] according to Figure 1 In process P20, a metal-containing film may be formed using a CVD process or an ALD process. The source for forming the metal-containing film, which includes the organometallic addition compound according to the embodiment, may be suitable for a chemical deposition process such as a CVD process or an ALD process.

[0048] When a source for forming a metal-containing film is used in a chemical deposition process, the composition of the source for forming the metal-containing film can be appropriately selected according to the delivery method. A gas delivery method or a liquid delivery method can be used as the delivery method. When the gas delivery method is used, the source for forming the metal-containing film can be evaporated to generate vapor by heating and / or reducing pressure in a storage container (hereinafter referred to as a "source container") in which a source for forming a metal-containing film is stored. The vapor can be introduced into a chamber (hereinafter referred to as a "deposition chamber") in which the substrate is loaded together with a carrier gas (for example, argon, nitrogen or helium) used as needed. When the liquid delivery method is used, the source for forming the metal-containing film can be delivered to an evaporator in a liquid or solution state, and heated and / or reduced pressure and evaporated in the evaporator to generate vapor, which can be introduced into the deposition chamber.

[0049] When based on Figure 1 When the process P20 uses a gas transport method to form a metal-containing film, the organometallic addition compound represented by the general formula (I) itself can be used as a source for forming the metal-containing film. Figure 1 When forming the metal-containing film using a liquid delivery method in step P20, the organometallic addition compound represented by the general formula (I) itself or a solution in which the organometallic addition compound represented by the general formula (I) is dissolved in an organic solvent can be used as a source for forming the metal-containing film. The source for forming the metal-containing film may also include other precursors, nucleophiles, etc.

[0050] In one embodiment, a multi-component CVD process can be used to form a metal-containing film in a method of manufacturing an IC device according to an embodiment. The multi-component CVD process can be performed by using the following methods: a method of independently evaporating and supplying each component of a source for forming a metal-containing film (hereinafter referred to as a "single source method"), or a method of evaporating and supplying a source mixture obtained by pre-mixing a multi-component source with a desired composition (hereinafter referred to as a "cocktail source method"). When using the cocktail source method, a mixture of an organometallic addition compound according to an embodiment and other precursors or a mixed solution obtained by dissolving the mixture in an organic solvent can be used as a source for forming a metal-containing film. The mixture or mixed solution may further contain a nucleophile.

[0051] The above-mentioned 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 flash point.

[0052] When an organic solvent is included in a source for forming a metal-containing film containing an organometallic addition compound according to an embodiment, the total amount of the organometallic addition compound according to an embodiment and other precursors in the organic solvent may be in the range 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, the total amount refers to the amount of the organometallic addition compound according to an embodiment when the source for forming a metal-containing film does not contain a metal compound and a semi-metallic compound other than the organometallic addition compound according to an embodiment, and refers to the sum of the amounts of the organometallic addition compound according to an embodiment and other precursors when the source for forming a metal-containing film contains the organometallic addition compound according to an embodiment and other metal compounds or semi-metallic compounds (i.e., other precursors).

[0053] In the method of manufacturing an IC device according to the embodiment, when a metal-containing film is formed using a multi-component CVD process, other precursors that can be used together with the organometallic addition compound according to the embodiment may include precursors suitable for forming a metal-containing film.

[0054] In one embodiment, other precursors that can be used to form a metal-containing film in the method of manufacturing an IC device according to the embodiment may include a composite of at least one organic coordination compound of alcohol compounds, diol compounds, β-diketone compounds, cyclopentadiene compounds, and organic amine compounds, silicon, and metal.

[0055] 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).

[0056] The alcohol compound that can be used as the organic coordination compound of other precursors may include, for example, alkyl alcohols such as methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, isobutanol, tert-butanol, pentanol, isopentanol 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.

[0057] Diol compounds that can be used as organic coordination compounds of other precursors may include, for example, 1,2-ethanediol, 1,2-propylene glycol, 1,3-propylene glycol, 2,4-hexanediol, 2,2-dimethyl-1,3-propylene glycol, 2,2-diethyl-1,3-propylene glycol, 1,3-butanediol, 2,4-butanediol, 2,2-diethyl-1,3-butanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,4-pentanediol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 2,4-hexanediol, and 2,4-dimethyl-2,4-pentanediol.

[0058] β-diketone compounds that can be used as other precursor organic coordination compounds 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, 2,2-dimethylheptane-3,5-dione, 2,6-dimethylheptane-3,5-dione, 2,2,6-trimethylheptane-3,5-dione, 2,2,6,6-tetramethylheptane-3,5-dione, octane-2,4-dione, 2,2,6-trimethyloctane-3,5-dione, 2,6-dimethyloctane-3,5-dione, 2,9-dimethylheptane-3,5 ... Methylnonane-4,6-dione, 2-methyl-6-ethyldecane-3,5-dione and 2,2-dimethyl-6-ethyldecane-3,5-dione; fluorine-substituted alkyl β-diketones such as 1,1,1-trifluoropentane-2,4-dione, 1,1,1-trifluoro-5,5-dimethylhexane-2,4-dione, 1,1,1,5,5,5-hexafluoropentane-2,4-dione and 1,3-diperfluorohexylpropane-1,3-dione; and ether-substituted β-diketones such as 1,1,5,5-tetramethyl-1-methoxyhexane-2,4-dione, 2,2,6,6-tetramethyl-1-methoxyheptane-3,5-dione and 2,2,6,6-tetramethyl-1-(2-methoxyethoxy)heptane-3,5-dione.

[0059] The cyclopentadiene compounds that can be used as organic coordination compounds of other precursors may include, for example, cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, sec-butylcyclopentadiene, isobutylcyclopentadiene, tert-butylcyclopentadiene, dimethylcyclopentadiene and tetramethylcyclopentadiene.

[0060] Organic amine compounds that can be used as organic coordination compounds of other precursors may include, for example, methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, ethylmethylamine, propylmethylamine, and isopropylmethylamine.

[0061] Other precursors can be suitable materials, and the method for preparing other precursors can be suitable methods. In one embodiment, when using alcohol compound as organic ligand, precursor can be prepared by reacting the inorganic salt of the above-mentioned element or its hydrate with the alkali metal alkoxide of corresponding alcohol compound. In one embodiment, the inorganic salt of the above-mentioned element or its hydrate can include, for example, metal halide or metal nitrate. Alkali metal alkoxide can include, for example, sodium alkoxide, lithium alkoxide and potassium alkoxide.

[0062] When a single-source method is used, the other precursors may include compounds having similar thermal and / or oxidative decomposition behaviors to the organometallic addition compound according to the embodiment. When a cocktail-source method is used, the other precursors may include materials having similar thermal and / or oxidative decomposition behaviors to the organometallic addition compound according to the embodiment, and may not deteriorate due to chemical reactions when mixed with the organometallic addition compound according to the embodiment.

[0063] In one embodiment, in order to form a metal-containing film using the method for manufacturing an IC device according to the embodiment, the source for forming the metal-containing film may include a nucleophile. The nucleophile may provide stability to the organometallic addition compound and / or other precursor containing a niobium atom, a tantalum atom, or a vanadium atom according to the embodiment. The nucleophile may include, for example, glycol ethers such as glycol dimethyl ether, diglycol dimethyl ether, triglycol dimethyl ether, and tetraglycol dimethyl ether; crown ethers such as 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8, and dibenzo-24-crown-8; polyamines such as ethylenediamine, N,N'-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylene Hexamine, 1,1,4,7,7-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine and triethoxytriethyleneamine; cyclic polyamines such as cyclam and cyclen; heterocyclic compounds such as pyridine, pyrrolidine, piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1,4-dimethoxy-1,4-diol; alkyl, The nucleophile can be used in an amount of about 0.1 mol to about 10 mol, for example, about 1 mol to about 4 mol, based on 1 mol of the total amount of the precursor.

[0064] In the source for forming a metal-containing film used to form a metal-containing film by using the method for manufacturing an IC device according to the embodiment, it may be useful to suppress the amount of impurity metal elements, impurity halogens (e.g., impurity chlorine) and impurity organic materials as much as possible. In one embodiment, a metal in an amount of about 100 ppb or less may be included in the source for forming the metal-containing film as an impurity metal element. In one embodiment, a metal in an amount of about 10 ppb or less may be included in the source for forming the metal-containing film as an impurity metal element. In one embodiment, the total amount of impurity metals in an amount of about 1 ppm or less, for example, about 100 ppb or less may be included in the source for forming the metal-containing film. 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 integrated (LSI) device, it may be useful to minimize the content of alkali metal elements and alkaline earth metal elements, which affect the electrical characteristics of the resulting film. In one embodiment, an impurity halogen component in an amount of about 100 ppm or less, for example, about 10 ppm or less or about 1 ppm or less may be included in the source for forming the metal-containing film.

[0065] The impurity organic component may be included in the source for forming the metal-containing film in an amount of about 500 ppm or less, for example, about 50 ppm or less, or about 10 ppm or less, based on the total amount of the source for forming the metal-containing film.

[0066] Moisture in the source used to form the metal-containing film may cause particles in the source used to form the metal-containing film, or may cause particles during the film formation process. In one embodiment, moisture can be removed from each of the precursor, organic solvent, and nucleophilic agent before use. The moisture content of each of the precursor, organic solvent, and nucleophilic agent can be less than about 10 ppm, for example, less than about 1 ppm.

[0067] When forming a metal-containing film using the method for manufacturing an IC device according to an 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 by particles. In one embodiment, when measuring particles in a liquid state using a light scattering particle detector, the number of particles having a size greater than about 0.3 μm can be adjusted to 100 or less in 1 ml of liquid. In one embodiment, the number of particles having a size greater than about 0.2 μm can be adjusted to 1,000 or less in 1 ml of liquid, and in one example, to 100 or less.

[0068] exist Figure 1In process P20, forming a metal-containing film using a source for forming a metal-containing film may include: evaporating the source for forming the 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 film on the substrate, and reacting the precursor 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.

[0069] 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, cocktail source method, or the like may be used.

[0070] 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.

[0071] The oxidizing gas may include, for example, O2, O3, O2 plasma, H2O, NO2, NO, N2O, CO, CO2, H2O2, HCOOH, CH3COOH, (CH3CO)2O, alcohols, peroxides, sulfur oxides, or combinations thereof.

[0072] The reducing gas may include, for example, H2.

[0073] The nitriding gas may include, for example, NH 3 , N 2 plasma, monoalkylamine, dialkylamine, trialkylamine, an organic amine compound (eg, alkylenediamine), a hydrazine compound, or a combination thereof.

[0074] When Figure 1 When forming a metal oxide film containing niobium atoms, tantalum atoms, or vanadium atoms in process P20, an oxidizing gas may be used as a reactive gas. Figure 1 When forming a metal nitride film containing niobium atoms, tantalum atoms, or vanadium atoms in process P20, a nitriding gas may be used as a reactive gas.

[0075] In one embodiment, Figure 1 In process P20, a metal-containing film containing niobium atoms, tantalum atoms, or vanadium atoms can be formed by using the following processes: a thermal CVD process in which a source gas containing an organic metal addition compound according to the embodiment, or both a source gas and a reactive gas, react to form a thin film only due to heating, a plasma CVD process using heat and plasma, a photo CVD process using heat and light, a photo-plasma CVD process using heat, light, and plasma, or an ALD process.

[0076] When based on Figure 1When forming a metal-containing film in process P20, the reaction temperature (or substrate temperature), reaction pressure, deposition rate, etc. may be appropriately selected based on the desired thickness and type of the desired metal-containing film. The reaction temperature may be a temperature at which the source used to form the metal-containing film can sufficiently react. In one embodiment, the reaction temperature may be in the range of room temperature to about 500° C., for example, about 150° C. to about 400° C.

[0077] When using the ALD process according to Figure 1 In the process of forming a metal-containing film in process P20, the film thickness of the metal-containing film can be controlled by adjusting the number of cycles of the ALD process. Forming a metal-containing film on a substrate using the ALD process may include: a source gas introduction process in which vapor formed by evaporating a source for forming a metal-containing film including an organometallic addition compound according to an embodiment is introduced into a deposition reactor; a precursor film formation process in which a precursor film is formed on the surface of the substrate using the vapor; an exhaust process in which unreacted source gas remaining on the substrate is exhausted from the reaction space; and a process in which the precursor film is chemically reacted with a reactive gas to form a metal-containing film on the surface of the substrate.

[0078] In one embodiment, the process of evaporating the source for forming the metal-containing film may be performed in a source container or an evaporator. The process of evaporating the source for forming the metal-containing film may be performed at a temperature of about 0° C. to about 200° C. When evaporating the source for forming the metal-containing film, the internal pressure of the source container or the evaporator may be in a range of about 1 Pa to about 10,000 Pa.

[0079] Figure 2 Detailed flowchart of a method for forming a metal-containing film by using a method for manufacturing an IC device according to an exemplary embodiment. Figure 2 Description based on Figure 1 Process P20 is a method of forming a metal-containing film by using an ALD process.

[0080] Reference Figure 2 In process P21, a source gas including an organometallic addition compound having a structure of formula (I) may be evaporated.

[0081] In one embodiment, the source gas may include the source described above for forming the metal-containing film. The process of evaporating the source gas may be performed at a temperature of about 0° C. to about 200° C. When evaporating the source gas, the internal pressure of the source container or evaporator may be in a range of about 1 Pa to about 10,000 Pa.

[0082] In process P22, the source gas evaporated according to process P21 may be supplied onto the substrate, thereby forming a metal source adsorption layer containing niobium atoms, tantalum atoms, or vanadium atoms on the substrate. In this case, the reaction temperature may be in a range from room temperature to about 500° C., for example, from about 150° C. to about 400° C. The reaction pressure may be in a range from about 1 Pa to about 10,000 Pa, for example, from about 10 Pa to about 1,000 Pa.

[0083] By supplying the evaporated source gas onto the substrate, an adsorption layer including a chemical adsorption layer and a physical adsorption layer of the evaporated source gas may be formed on the substrate.

[0084] In process P23 , unwanted byproducts remaining on the substrate may be removed by supplying a purge gas onto the substrate.

[0085] In one embodiment, an inert gas such as argon (Ar), helium (He), or neon (Ne), or nitrogen (N 2 ) may be used as the purge gas.

[0086] In one embodiment, instead of purging the gas, the reaction space may be evacuated by reducing the pressure of the reaction space in which the substrate is loaded. In this case, to reduce the pressure of the reaction chamber, 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.

[0087] 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 a reaction chamber containing the substrate may be performed. The annealing process may be performed at a temperature ranging from room temperature to about 500° C., for example, at a temperature ranging from about 50° C. to about 400° C.

[0088] 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 at an atomic level.

[0089] In one embodiment, when a metal oxide film including niobium atoms, tantalum atoms, or vanadium atoms is formed on a substrate, the reactive gas may be an oxidizing gas, for example, O2, O3, O2 plasma, H2O, NO2, NO, N2O, CO, CO2, H2O2, HCOOH, CH3COOH, (CH3CO)2O, alcohols, peroxides, sulfur oxides, or combinations thereof.

[0090] In one embodiment, when a metal nitride film including niobium atoms, tantalum atoms, or vanadium atoms is formed on a substrate, the reactive gas may include, for example, NH3, N2 plasma, monoalkylamines, dialkylamines, trialkylamines, organic amine compounds, hydrazine compounds, and combinations thereof.

[0091] In one embodiment, the reactive gas may be a reducing gas, such as H2.

[0092] In process P24, the reaction space may be maintained at a temperature between room temperature and about 500° C., for example, between about 50° C. and about 400° C., or between about 50° C. and about 200° C., so that the metal source adsorption layer containing niobium atoms, tantalum atoms, or vanadium atoms can fully react with the reactive gas. In process P24, the pressure of the reaction space may be in a range of about 1 Pa to about 10,000 Pa, for example, about 10 Pa to about 1,000 Pa.

[0093] In process P24, the reactive gas may be treated with plasma. During the plasma treatment process, a radio frequency (RF) output may be in the range of about 0W to about 1,500W, for example, about 50W to about 600W.

[0094] In process P25 , unwanted byproducts remaining on the substrate may be removed by supplying a purge gas onto the substrate.

[0095] In one embodiment, an inert gas such as argon (Ar), helium (He), or neon (Ne), or nitrogen (N 2 ) may be used as the purge gas.

[0096] In process P26, you can repeat Figure 2 Processes P21 to P25 are repeated until the metal-containing film is formed to a desired thickness.

[0097] A thin film deposition process including a series of processes, such as processes P21 to P25, may be defined as one cycle, and the cycle may be repeated multiple times until the metal-containing film is formed to a desired thickness. In one embodiment, after the cycle is performed once, unreacted gas may be exhausted from the reaction chamber by performing a purge gas exhaust process similar to process P23 or P25, and then a subsequent cycle may be performed.

[0098] 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 can 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 properties of the resulting metal-containing film may be degraded. If the deposition rate of the metal-containing film is too low, productivity is reduced. In one embodiment, the deposition rate of the metal-containing film may be in the range of about 0.01 nm / min to about 100 nm / min, for example, about 1 nm / min to about 50 nm / min.

[0099] Reference Figure 2 The described method of forming the metal-containing film is merely an example, and various modifications and changes in the method may be made.

[0100] In one embodiment, to form a metal-containing film on a substrate, at least one of other precursors, reactive gases, carrier gases, and purge gases may be supplied to the substrate simultaneously or sequentially with the organometallic addition compound represented by the general formula (I). Details of other precursors, reactive gases, carrier gases, and purge gases that may be supplied to the substrate together with the organometallic addition compound represented by the general formula (I) are as described above.

[0101] In one embodiment, referring to Figure 2 In the described process of forming the metal-containing film, a reactive gas may be supplied onto the substrate between processes P21 to P25.

[0102] Figures 3A to 3D is a schematic diagram of the configuration of deposition systems 200A, 200B, 200C, and 200D that may be used to form a metal-containing film in a method of manufacturing an IC device according to an exemplary embodiment.

[0103] Figures 3A to 3D Each of the illustrated deposition systems 200A, 200B, 200C, and 200D 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 a substrate W by using a process gas supplied by a source container 212 included in the fluid delivery unit 210; and an exhaust system 270 configured to exhaust gases or byproducts that may remain after a reaction occurs in the thin film forming unit 250.

[0104] The thin film forming unit 250 may include a reaction chamber 254 including a susceptor 252 configured to support a substrate W. A shower head 256 may be installed at a top unit inside the reaction chamber 254. The shower head 256 may be configured to supply a gas supplied by the fluid delivery unit 210 onto the substrate W.

[0105] The fluid transport 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 via a bypass line 226. A valve V3 may be installed at the bypass line 226. The valve V3 may be operated by pneumatic pressure using an electric motor or other remote control unit.

[0106] The source compound supplied from the source container 212 may be supplied to the reaction chamber 254 through the inlet line 266 of the thin film forming unit 250 connected to the outlet line 224 of the fluid transport unit 210. When necessary, the source compound supplied from the source container 212 may be supplied to the reaction chamber 254 together with a carrier gas supplied through the inlet line 268. A valve V4 and an MFC M3 may be installed at the inlet line 268 to which the carrier gas is supplied.

[0107] The thin film forming unit 250 may include an inlet line 262 configured to supply a purge gas into the reaction chamber 254 and an inlet line 264 configured to supply a reactive gas. A valve V5 and an MFCM4 may be installed at the inlet line 262, and a valve V6 and an MFC M5 may be installed at the inlet line 264.

[0108] The process gas used in the reaction chamber 254 and the reaction byproducts to be discarded can 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 gas and reaction byproducts exhausted from the reaction chamber 254.

[0109] A trap 276 may be installed in the exhaust line 272 on the upstream side of the vacuum pump 274. The trap 276 may capture reaction byproducts generated, for example, by unreacted process gas in the reaction chamber 254 and prevent the reaction byproducts from flowing into the vacuum pump 274 provided on the downstream side.

[0110] The trap 276 installed at the exhaust line 272 can capture reaction byproducts that may be generated due to reactions between process gases, for example, and can prevent the reaction byproducts from flowing to the downstream side of the trap 276. The trap 276 can be configured to be cooled by a cooler or a water cooling device.

[0111] 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. A valve V7 may be installed at the bypass line 278, and a valve V8 may be installed at a portion of the discharge line 272 that may extend parallel to the bypass line 278.

[0112] As in Figure 3A and 3C As in the deposition systems 200A and 200C shown, a heater 214 may be installed in the source container 212. The heater 214 may maintain the source compound contained in the source container 212 at a relatively high temperature.

[0113] As in Figure 3B and 3DAs in the illustrated deposition systems 200B and 200D, an evaporator 258 may be installed at the inlet line 266 of the thin film forming unit 250. The evaporator 258 may evaporate the fluid supplied in a liquid state by the fluid transport unit 210 and supply the evaporated source compound into the reaction chamber 254. The source compound evaporated by the evaporator 258 may be supplied to the reaction chamber 254 together with a carrier gas supplied through the inlet line 268. The supply of the source compound into the reaction chamber 254 through the evaporator 258 may be controlled by a valve V9.

[0114] In one embodiment, as in Figure 3C and 3D As in the illustrated deposition systems 200C and 200D, in order to generate plasma in the reaction chamber 254 , 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 .

[0115] In one embodiment, Figures 3A to 3D As shown, deposition systems 200A, 200B, 200C, and 200D may be configured such that one source container 212 is connected to a 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 a reaction chamber 254. The number of source containers 212 connected to a reaction chamber 254 may be any suitable number.

[0116] In one embodiment, the Figure 3B and 3D The evaporator 258 in either of the illustrated deposition systems 200B and 200D evaporates a source for forming a metal-containing film comprising an organometallic addition compound of formula (I).

[0117] In reference Figure 1 and 2 The method of manufacturing an IC device described herein may be used Figures 3A to 3D Any of the deposition systems 200A, 200B, 200C, and 200D shown forms a metal-containing film on a substrate W. To form the metal-containing film on the substrate W, the organometallic addition compound of formula (I) according to the embodiment can be transported by using various methods and supplied to a reaction space of the thin film forming system, for example, to a substrate. Figures 3A to 3D In the reaction chamber 254 of each of the deposition systems 200A, 200B, 200C and 200D shown.

[0118] In one embodiment, in order to Figure 1 and 2 The method described for forming a metal-containing film can be performed by using a batch type apparatus instead of a single type apparatus, such as Figures 3A to 3D Deposition systems 200A, 200B, 200C, and 200D are shown for simultaneously forming metal-containing films on multiple substrates.

[0119] When a metal-containing film is formed by using the method of manufacturing an IC device according to the embodiment, conditions for forming the metal-containing film may include a reaction temperature (or substrate temperature), a reaction pressure, and a deposition rate.

[0120] The reaction temperature may be a temperature at which the organometallic addition compound according to the embodiment, for example, the organometallic addition compound of formula (I) can react sufficiently. In one embodiment, the reaction temperature may be a temperature of about 150° C. or higher. In one embodiment, the reaction temperature may be selected within the range of about 150° C. to about 400° C. or within the range of about 200° C. to about 350° C.

[0121] In one embodiment, in the case of a thermal CVD process or a photoCVD process, the reaction pressure may be selected within a range of about 10 Pa to atmospheric pressure, and in the case of a plasma CVD process, the reaction pressure may be selected within a range of about 10 Pa to about 2,000 Pa.

[0122] The deposition rate can be controlled by adjusting the conditions for supplying the source compound (e.g., evaporation temperature and evaporation pressure), the reaction temperature, and the reaction pressure. In one embodiment, in the method for manufacturing an IC device according to the embodiment, the deposition rate of the metal-containing film can be selected within a range of about 0.01 nm / min to about 100 nm / min, for example, within a range of about 1 nm / min to about 50 nm / min. When the metal-containing film is formed using an ALD process, the number of ALD process cycles can be adjusted to control the thickness of the metal-containing film.

[0123] In one embodiment, when forming a metal-containing film using an ALD process, energy (e.g., plasma, light, or voltage) may be applied. The time period for applying the energy may be selected differently. In one embodiment, energy (e.g., plasma, light, or voltage) may be applied when a source gas containing 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 exhaust, when a reactive gas is introduced into the reaction chamber, or between various time periods for performing the above processes.

[0124] In one embodiment, after forming a metal-containing film using the organometallic addition compound of formula (I), the metal-containing film may be annealed under an inert atmosphere, an oxidizing atmosphere, or a reducing atmosphere. In one embodiment, the metal-containing film may be reflowed to remove surface roughness. Each of the annealing and reflow processes may be performed at a temperature of about 200°C to about 1,000°C, for example, about 250°C to about 500°C.

[0125] In one embodiment, various types of metal-containing films can be formed by appropriately selecting the organometallic addition compound according to the embodiment, other precursors that can be used with the organometallic addition compound, reactive gases, and conditions for forming the film. In one embodiment, the metal-containing film formed using the method according to the embodiment may contain 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 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 include, for example, a Nb-Hf alloy or a Nb-Ti alloy. The tantalum alloy film may include, for example, a Ta-Ti alloy or a Ta-W alloy. The metal-containing film formed using the method according to the embodiment can be used as a material for each component included in an IC device. In one embodiment, the metal-containing film can be used for electrode materials of dynamic random access memory (DRAM) devices, gates of transistors, resistors, anti-magnetic films for hard device recording layers, catalyst materials for solid polymer fuel cells, conductive barrier films for metal wires, dielectric films for capacitors, barrier metal films for liquid crystals, elements for thin-film solar cells, elements for semiconductor devices, nanostructures, etc.

[0126] Figures 4A to 4J In the manufacturing of IC devices according to the embodiment (refer to Figure 4J Cross-sectional views of various stages in the method of 300).

[0127] Reference Figure 4A , an interlayer dielectric 320 may be formed on the substrate 310 including the plurality of active regions AC. Thereafter, a plurality of conductive regions 324 may be formed to pass through the interlayer dielectric 320 and be connected to the plurality of active regions AC.

[0128] 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 a conductive region, such as a doped well or a doped structure. The multiple active regions AC may be defined by multiple device isolation regions 312 formed in the substrate 310. The device isolation region 312 may include a silicon oxide film, a silicon nitride film, a silicon oxynitride film, or a combination thereof. The interlayer dielectric 320 may include a silicon oxide film. The multiple conductive regions 324 may be connected to one terminal of a switching device (e.g., a field effect transistor) formed on the substrate 310. The multiple conductive regions 324 may include polysilicon, metal, conductive metal nitride, metal silicide, or a combination thereof.

[0129] Reference Figure 4B , an insulating layer 328 covering the interlayer dielectric 320 and the plurality of conductive regions 324 may be formed. The insulating layer 328 may serve as an etch stop layer. The insulating layer 328 may include a mold film 330 (see FIG. 1 ) formed in a subsequent process relative to the interlayer dielectric 320. Figure 4C ) An insulating material with etching selectivity. The insulating layer 328 may include silicon nitride, silicon oxynitride, or a combination thereof.

[0130] Reference Figure 4C , a mold film 330 may be formed on the insulating layer 328 .

[0131] The mold film 330 may include an oxide film. In one embodiment, the mold film 330 may include an oxide film, for example, borophosphosilicate glass (BPSG), phosphosilicate 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 thickness of the mold film 330 may be, for example, about 1000 Å. to about In one embodiment, the mold film 330 may include a support film. The support film may include a material having an etching selectivity relative to the mold film 330. The support film may include a material having a lower etching rate relative to an etching atmosphere when removing the mold film 330 in a subsequent process, for example, relative to an etchant including ammonium fluoride (NH4F), hydrofluoric acid (HF), and water. In one embodiment, the support film may include silicon nitride, silicon carbonitride, tantalum oxide, titanium oxide, or a combination thereof.

[0132] Reference Figure 4D , a sacrificial film 342 and a mask pattern 344 may be sequentially formed on the mold film 330 .

[0133] The sacrificial film 342 may include an oxide film. The mask pattern 344 may include an oxide film, a nitride film, a polysilicon film, a photoresist film, or a combination thereof. The region where the lower electrode of the capacitor is to be formed may be defined by the mask pattern 344.

[0134] Reference Figure 4E , the sacrificial film 342 and the mold film 330 may be dry-etched using the mask pattern 344 as an etching mask and the insulating layer 328 as an etch stop layer, thereby forming a sacrificial pattern 342P and a mold pattern 330P defining a plurality of holes H1. In one embodiment, the insulating layer 328 may also be etched due to overetching, thereby forming an insulating pattern 328P exposing the plurality of conductive regions 324.

[0135] Reference Figure 4F , can be obtained from Figure 4E The mask pattern 344 is removed from the resultant, and then a conductive film 350 for forming a lower electrode is formed, which fills the plurality of holes H1 and covers the exposed surfaces of the sacrificial pattern 342P.

[0136] The conductive film 350 used to form the lower electrode may include a doped semiconductor, a conductive metal nitride, a metal, a metal silicide, a conductive oxide, or a combination thereof. In one embodiment, the conductive film 350 used to form 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 used to form the lower electrode, a CVD, metal organic CVD (MOCVD), or ALD process may be used.

[0137] In one embodiment, to form the conductive film 350 for forming the lower electrode, a Figure 1 Process P20 or refer to Figure 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 formed using Figure 1 Process P20 or refer to Figure 2 The membrane formed by the method described can be used Figures 3A to 3D The conductive film 350 for forming the lower electrode is formed using any one of the deposition systems 200A, 200B, 200C, and 200D shown.

[0138] Reference Figure 4G, the upper side of the conductive film 350 for forming a lower electrode may be partially removed, thereby dividing the conductive film 350 for forming a lower electrode into a plurality of lower electrodes LE.

[0139] To form the plurality of lower electrodes LE, a portion of the upper side of the conductive film 350 for forming the lower electrodes and the sacrificial pattern 342P (see FIG. 1 ) may be removed by using an etch-back or chemical mechanical polishing (CMP) process. Figure 4F ), so that the upper surface of the mold pattern 330P is exposed.

[0140] Reference Figure 4H , can be obtained from Figure 4G The mold pattern 330P is removed by the resultant to expose 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 (NH4F), hydrofluoric acid (HF), and water.

[0141] Reference Figure 4I , a dielectric film 360 may be formed on the plurality of lower electrodes LE.

[0142] The dielectric film 360 may conformally cover exposed surfaces of the plurality of lower electrodes LE.

[0143] In one embodiment, the dielectric film 360 may include hafnium oxide, hafnium oxynitride, hafnium silicon oxide, zirconium oxide, zirconium silicon oxide, tantalum oxide, titanium oxide, barium strontium titanium oxide, barium titanium oxide, strontium titanium oxide, yttrium oxide, aluminum oxide, scandium tantalum oxide, lead zinc niobate, or a combination thereof. The dielectric film 360 may be formed by an ALD process. In one embodiment, to form at least a portion of the dielectric film 360, a Figure 1 Process P20 or refer to Figure 2 In one embodiment, the dielectric film 360 may include a tantalum oxide film, which may be formed using a Figure 1 Process P20 or refer to Figure 2 The membrane formed by the method described can be used Figures 3A to 3D The dielectric film 360 may be formed by using any of the deposition systems 200A, 200B, 200C, and 200D shown. The dielectric film 360 may have a thickness of approximately to about thickness.

[0144] In one embodiment, as referenced Figure 4I Before forming the dielectric film 360 on the plurality of lower electrodes LE, a process of forming a lower interface film to cover the surface of each of the plurality of lower electrodes LE may be further 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 containing niobium, tantalum, or vanadium. Figure 1Process P20 or refer to Figure 2 The method described forms a metal-containing film included in the lower interface film. Figures 3A to 3D Any of the deposition systems 200A, 200B, 200C, and 200D shown is used to form the lower interface film.

[0145] Reference Figure 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 .

[0146] The upper electrode UE may include a doped semiconductor, a conductive metal nitride, a metal, a metal silicide, a conductive oxide, or a combination thereof. In one embodiment, the upper electrode UE may include: 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.

[0147] In one embodiment, to form the upper electrode UE, the Figure 1 Process P20 or refer to Figure 2 The method described herein forms a metal-containing film. Figures 3A to 3D The upper electrode UE is formed using any one of the deposition systems 200A, 200B, 200C, and 200D shown.

[0148] In one embodiment, as referenced Figure 4J Before forming the upper electrode UE on the dielectric film 360, a process of forming an upper interface film to cover the surface of the dielectric film 360 may be further 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 containing niobium, tantalum, or vanadium. Figure 1 Process P20 or refer to Figure 2 The method described forms a metal-containing film included in the upper interface film. Figures 3A to 3D Any of the deposition systems 200A, 200B, 200C, and 200D shown is used to form the upper interface film.

[0149] In one embodiment, in a method of manufacturing IC device 300, as shown in FIG. Figures 4A to 4J As shown, 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 cross-sectional structure with a blocked bottom or a cylindrical cross-sectional structure.

[0150] By using the reference Figures 4A to 4J In the IC device 300 manufactured by the described method, the capacitor 370 may include a lower electrode LE having a 3D electrode structure. In order to compensate for the decrease in capacitance due to the reduction in design rules, the aspect ratio of the lower electrode LE having a 3D structure is increased, and a dielectric film 360 with good quality can be formed in a deep and narrow 3D space using an ALD process. Figures 4A to 4J In the method of manufacturing the IC device 300 according to the embodiment described, 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, thereby improving process stability.

[0151] The following examples and comparative examples are provided to highlight the characteristics 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 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.

[0152] Synthesis example 1

[0153] Synthesis of compounds of formula 2

[0154] Under an argon (Ar) atmosphere, 9.40 g (50.0 mmol) of niobium pentafluoride and 250 mL of anhydrous dichloromethane were placed in a 500-mL four-necked flask and stirred while maintaining the resulting liquid at approximately 25°C. Subsequently, 17.7 g (51.5 mmol) of tris(2,2,2-trifluoroethyl) phosphate was added dropwise at ambient temperature and stirred for approximately 5 hours. The solvent and unreacted tris(2,2,2-trifluoroethyl) phosphate were distilled under reduced pressure, followed by purification by distillation, yielding 10.2 g of the desired product (yield 38.2%).

[0155] (Analytical value)

[0156] (1) 1H-NMR (heavy benzene)

[0157] 3.70ppm (6H, multiple peaks)

[0158] (2) Elemental analysis (theoretical value)

[0159] 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%)

[0160] Synthesis example 2

[0161] Synthesis of compound of formula 6

[0162] Under an argon atmosphere, 13.5 g (50.0 mmol) of niobium pentachloride and 300 mL of anhydrous dichloromethane were placed in a 500-mL four-necked flask and stirred while maintaining the resulting liquid at approximately 25°C. Subsequently, 17.7 g (51.5 mmol) of tris(2,2,2-trifluoroethyl) phosphate was added dropwise at ambient temperature and stirred for approximately 5 hours. The solvent and unreacted tris(2,2,2-trifluoroethyl) phosphate were distilled under reduced pressure, followed by purification by distillation, yielding 28.0 g of the desired product (yield 91.2%).

[0163] (Analytical value)

[0164] (1) 1H-NMR (heavy benzene)

[0165] 3.87ppm (6H, doublet of four peaks)

[0166] (2) Elemental analysis (theoretical value)

[0167] 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%)

[0168] Synthesis example 3

[0169] Synthesis of compound of formula 7

[0170] Under an argon atmosphere, 13.5 g (50.0 mmol) of niobium pentachloride and 300 mL of anhydrous dichloromethane were placed in a 500-mL four-necked flask and stirred while maintaining the resulting liquid at approximately 25°C. Subsequently, 28.2 g (51.5 mmol) of tris(1,1,1,3,3,3-hexafluoro-2-propyl) phosphate was added dropwise at ambient temperature and stirred for approximately 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 20.5 g of the desired product (yield 50.2%).

[0171] (Analytical value)

[0172] (1) 1H-NMR (heavy benzene)

[0173] 4.81ppm (3H, singlet, broad)

[0174] (2) Elemental analysis (theoretical value)

[0175] 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%)

[0176] Synthesis example 4

[0177] Synthesis of compounds of formula 14

[0178] Under an argon atmosphere, 17.9 g (50.0 mmol) of TaCl5 and 300 mL of anhydrous dichloromethane were placed in a 500-mL 4-necked flask and stirred while maintaining the resulting liquid at a temperature of approximately 25°C. Subsequently, 17.7 g (51.5 mmol) of tris(2,2,2-trifluoroethyl) phosphate was added dropwise at ambient temperature and stirred for approximately 5 hours. The solvent and unreacted tris(2,2,2-trifluoroethyl) phosphate were distilled under reduced pressure and then purified by distillation to obtain 30.9 g of the target product (yield 87.9%).

[0179] (Analytical value)

[0180] (1) 1H-NMR (heavy benzene)

[0181] 3.85ppm (6H, doublet of four peaks)

[0182] (2) Elemental analysis (theoretical value)

[0183] 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%)

[0184] Examples 1 to 4 and Comparative Examples 1 to 4

[0185] Next, the thermogravimetric-differential thermal analysis (TG-DTA) 50% mass reduction temperature T1 (at normal pressure), phase (at 25°C) and melting point of each of the compounds of Formulas 2, 6, 7 and 14 obtained in Synthesis Examples 1 to 4 and the following comparative compounds 1 to 4 were measured as follows.

[0186]

[0187] "nBu" refers to n-butyl.

[0188] (1) TG-DTA at normal pressure

[0189] The 50% mass reduction temperature T1 of each of the compounds of Formulas 2, 6, 7 and 14 obtained in Synthesis Examples 1 to 4 and Comparative Compounds 1 to 4 was measured using TG-DTA technology under the conditions of normal pressure, an Ar flow rate of 100 mL / min, a heating rate of 10°C / min and a scanning temperature range of about 30°C to about 600°C, and the measurement results are shown in Table 1.

[0190] (2) Melting point of the compound

[0191] The results obtained by visually observing the phases of the compounds of Formulas 2, 6, 7, and 14 obtained in Synthesis Examples 1 to 4 and Comparative Compounds 1 to 4 at a temperature of about 25° C. are shown in Table 1. Table 1 also shows the results obtained by measuring the melting points of the compounds that were solid at a temperature of about 25° C.

[0192] [Table 1]

[0193]

[0194] According to the results in Table 1, the 50% mass reduction temperature T1 of each of the compounds of Formulas 2, 6, 7, and 14 measured using the TG-DTA technique at normal pressure is about 215° C. or less. Therefore, the compounds of Formulas 2, 6, 7, and 14 have a high vapor pressure. In addition, all of the compounds of Formulas 2, 6, 7, and 14 are liquid at a temperature of about 25° C. and have a melting point lower than about 25° C.

[0195] In contrast, each of Comparative Compounds 1 to 4 has a relatively high melting point of about 115°C 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°C, and therefore, Comparative Compounds 1 and 3 are compounds having a relatively high vapor pressure similar to that of the compound according to the embodiment. However, Comparative Compounds 1 and 3 have very high melting points of about 205°C or higher.

[0196] Examples 5 to 8 and Comparative Examples 5 to 8 (Formation of Metal-Containing Film)

[0197] Next, each of the compounds of Formulas 2, 6, 7, and 14 obtained in Synthesis Examples 1 to 4 and Comparative Compounds 1 to 4 was used as a source and Figure 3A A niobium nitride film or a tantalum nitride film is formed on a silicon substrate using an ALD deposition system. The conditions for the ALD process for forming the niobium nitride film or the tantalum nitride film are as follows.

[0198] <Condition>

[0199] Reaction temperature (substrate temperature): 250°C

[0200] Reactive gas: ammonia

[0201] <Process>

[0202] One cycle including a series of processes (1) to (4) described below was repeated 150 times under the above conditions.

[0203] Process (1): Under conditions where a source container is heated to a temperature of about 90° C. and maintained at an internal pressure of about 100 Pa, vapor is generated by an evaporation source, the vapor is introduced into a chamber, and a niobium nitride film or a tantalum nitride film is deposited in the chamber maintained at a pressure of about 100 Pa for about 30 seconds.

[0204] Process (2): An argon (Ar) purge process was performed for about 10 seconds to remove unreacted sources from the chamber.

[0205] Process (3): Reactive gas is supplied into the chamber at a pressure of about 100 Pa to induce a reaction for about 30 seconds.

[0206] Process (4): An argon purge process was performed for about 10 seconds to remove unreacted sources from the chamber.

[0207] The thickness of each of the thin films obtained by processes (1) to (4) was measured using an X-ray reflectivity 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 obtained thin films was measured using an X-ray photoelectron spectroscopy (XPS) technique, and the measurement results are shown in Table 2.

[0208] [Table 2]

[0209]

[0210] 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 the comparative compounds 2 and 4 is 6 atomic percent (atomic %) or more. In contrast, the carbon content of each of the thin films obtained using the compounds of Formulas 2, 6, 7, and 14 is about 0.1 atomic % (which is the detection limit) or less. Therefore, the thin films obtained using the compounds of Formulas 2, 6, 7, and 14 are thin films of 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 is about 3 nm or less, while each of the thin films obtained using the compounds of Formulas 2, 6, 7, and 14 is about 5.0 nm or more. It can be seen from this that the productivity of the thin film formation process is excellent.

[0211] As can be seen from the examples, the organometallic addition compounds according to Examples 1 to 8 have a low melting point and a high vapor pressure, and when the organometallic addition compounds are used as a source in an ALD process or a CVD process for forming a thin film, they help improve the productivity of the thin film forming process.

[0212] In summary and review, a source compound for forming a metal-containing film should provide excellent gap filling characteristics and step coverage characteristics during formation of a metal-containing film for manufacturing IC devices, and be advantageous in terms of process stability and mass manufacturability due to its ease of handling.

[0213] One or more embodiments may provide an organometallic addition compound comprising niobium, tantalum, or vanadium as a metal.

[0214] One or more embodiments can provide an organometallic addition compound that can be used as a source compound that can provide excellent thermal stability, process stability, and mass productivity during the formation of a metal-containing film for manufacturing an integrated circuit (IC) device.

[0215] One or more embodiments may provide methods of manufacturing IC devices by which metal-containing films of good quality may be formed using metal-containing source compounds that provide excellent process stability and mass manufacturability, thereby providing desired electrical properties.

[0216] Example embodiments have been disclosed herein, and although specific terms are employed, they are used and are to be interpreted in a general and descriptive sense only, and not for purposes of limitation. In some cases, as will be apparent to one of ordinary skill in the art at the time of filing this application, features, characteristics, and / or elements described with respect to a specific embodiment may be used alone or in combination with features, characteristics, and / or elements described with respect to other embodiments, unless expressly stated otherwise. Therefore, it will be understood by those skilled in the art that various changes in form and detail may be made without departing from the spirit and scope of the invention as set forth in the appended claims.

Claims

1. An organometallic addition compound represented by the general formula (I): General formula (I) in, In the general formula (I), R 1 、R 2 and R 3 are each independently trifluoromethyl, trifluoroethyl, hexafluoroisopropyl or nonafluoro-tert-butyl, 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.

2. The 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.

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

4. The 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 R 1 、R 2 and R 3 are each independently hexafluoroisopropyl or nonafluoro-tert-butyl.

5. The 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 R 1 、R 2 and R 3 are each independently hexafluoroisopropyl or nonafluoro-tert-butyl.

6. The 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 R 1 、R 2 and R 3 Each is independently trifluoromethyl or nonafluoro-tert-butyl.

7. The 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 R 1 、R 2 and R 3 Each is independently trifluoromethyl or nonafluoro-tert-butyl.

8. The organometallic addition compound according to claim 1, wherein the organometallic addition compound is liquid at 20°C to 28°C.

9. A method for 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) in, In the general formula (I), R 1 、R 2 and R 3 are each independently trifluoromethyl, trifluoroethyl, hexafluoroisopropyl or nonafluoro-tert-butyl, 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.

10. The method of claim 9, wherein the organometallic addition compound is liquid at 20°C to 28°C.

11. The method according to claim 9, 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.

12. The method according to claim 9, wherein In the general formula (I), m is 5, and n is 1.

13. The method of claim 9, wherein forming the metal-containing film comprises: supplying the organometallic addition compound of formula (I) onto the substrate; and A reactive gas is supplied onto the substrate.

14. The method according to claim 13, wherein the reactive gas is NH3, N2 plasma, an organic amine compound, a hydrazine compound, or a combination thereof.

15. The method of claim 13, wherein the reactive gas is O2, O3, O2 plasma, H2O, NO2, NO, N2O, CO, CO2, H2O2, HCOOH, CH3COOH, (CH3CO)2O, alcohol, peroxide, sulfur oxide, or a combination thereof. The method according to claim 13 , wherein the reactive gas is H 2 .

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