Metal compound and method for manufacturing semiconductor device using the same

Abstract

Metal compounds and methods for making semiconductor devices using the same are described herein. The metal compound includes a material of Chemical Formula 1, wherein M is Nb or Ta; R is a substituted or unsubstituted C3-C10 alkyl group; and X 1 , X 2 , X 3 , X 4 and X 5 Each is independently selected from F, Cl, Br and I. [Chemical Formula 1] #imgabs0#

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Korean Patent Application No. 10-2019-0056596 filed on May 14, 2019, and Korean Patent Application No. 10-2019-0138404 filed on November 1, 2019, in the Korean Intellectual Property Office, the disclosures of which are incorporated herein in their entirety by reference. Technical Field

[0003] The present inventive concept relates to a metal compound and a method of manufacturing a semiconductor device using the same, and more particularly, to a deposition process using the metal compound of the present invention. Background Art

[0004] In recent years, the development of electronic technology has rapidly accelerated the miniaturization of semiconductor devices. For these reasons, the patterns of semiconductor devices have become complex and fine, which has led to more complex semiconductor manufacturing. There is an increasing demand for easy formation of thin layers to manufacture semiconductor devices. Summary of the invention

[0005] Some example embodiments of the present inventive concepts provide deposition precursors having ease of transport and stability.

[0006] Some example embodiments of the present inventive concepts provide a method of forming a thin metal layer, wherein the thin metal layer has a low resistivity.

[0007] According to some example embodiments of the present inventive concepts, the metal compound may include a material of Chemical Formula 1:

[0008] [Chemical formula 1]

[0009]

[0010] in:

[0011] M is Nb or Ta;

[0012] R is a substituted or unsubstituted C3-C10 alkyl group; and

[0013] X 1 , X 2 , X 3 , X 4 and X 5 Each is independently selected from F, Cl, Br and I.

[0014] According to some example embodiments of the present inventive concept, a method of manufacturing a semiconductor device may include: providing a deposition precursor; and forming a layer (e.g., a thin layer) using the deposition precursor. In some embodiments, the method includes preparing the deposition precursor. The deposition precursor may include a metal compound of Chemical Formula 1.

[0015] [Chemical formula 1]

[0016]

[0017] in:

[0018] M is Nb or Ta;

[0019] R is a substituted or unsubstituted C3-C10 alkyl group; and

[0020] X 1 , X 2 , X 3 , X 4 and X 5 Each is independently selected from F, Cl, Br and I. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 A flow chart illustrating a deposition process using a metal compound according to some example embodiments.

[0022] Figure 2 The illustration shows a schematic diagram of a deposition system according to some example embodiments.

[0023] Figure 3A and 3B A cross-sectional view illustrating a method of forming a thin layer according to some example embodiments is illustrated.

[0024] Figures 4A-4G A cross-sectional view illustrating a method of fabricating a semiconductor device according to some example embodiments is illustrated. DETAILED DESCRIPTION

[0025] As used herein in this specification, the language "unsubstituted or substituted" may mean unsubstituted or substituted by at least one substituent selected from the group consisting of a deuterium atom, a halogen atom, a cycloalkyl group, an aryl group, a heteroaryl group, a heteroalicyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a cyano group, a carbonyl group, an amino group, and any derivatives thereof. In addition, each substituent may be substituted or unsubstituted. For example, a haloalkyl group may be interpreted as an alkyl group substituted by a halogen.

[0026] As used herein in this specification, an alkyl group may be a straight chain, branched, or cyclic alkyl group. In particular, an alkyl group may be a straight chain or branched alkyl group. The number of carbon atoms in the alkyl group may be 1-10 (also referred to herein as a C1-C10 alkyl group), but the inventive concept is not limited thereto. For example, an alkyl group may include three to ten carbon atoms (also referred to herein as a C3-C10 alkyl group).

[0027] As used herein in this specification, the halogen element may include fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0028] Unless otherwise defined in this specification, when a chemical bond is not drawn at a position in a chemical formula for which a bond may exist, hydrogen may be bonded to the position. In this specification, room temperature may be a temperature of 25°C.

[0029] As used herein in this specification, like reference numerals may refer to like components.

[0030] The metal compound according to the present inventive concept and the method for making the same will now be described below. In some embodiments, the metal compound according to the present inventive concept is a coordination compound (eg, a transition metal nitrile complex).

[0031] According to the present inventive concept, the metal compound may be represented by Chemical Formula 1 below.

[0032] [Chemical formula 1]

[0033]

[0034] In Chemical Formula 1, M may be Nb or Ta, R may be an unsubstituted or substituted C3-C10 alkyl group, and X 1 , X 2 , X 3 , X 4 and X 5 They may each independently be one selected from F, Cl, Br and I.

[0035] In some embodiments, when R is a halogen-substituted alkyl group in Chemical Formula 1, the halogen of the halogen-substituted alkyl group may be F, Cl, Br, or I. For example, the halogen-substituted alkyl group may be a fluorine-substituted alkyl group or a chlorine-substituted alkyl group. In some embodiments, R may be an unsubstituted or substituted C4-C10 alkyl group.

[0036] In some embodiments, X 1 , X 2 , X 3 , X 4 and X 5 They may each independently be one selected from F and Cl.

[0037] The metal compound represented by Chemical Formula 1 may be one of the compounds selected from Group A.

[0038] [Compounds of Group A]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044] In compounds No. 1 to No. 78 of group A, Me is a methyl group, Et is an ethyl group, nPr is an n-propyl group, iPr is an isopropyl group, iBu is an isobutyl group, sBu is a sec-butyl group, and tBu is a tert-butyl group.

[0045] nPr may be represented by the following Chemical Formula 2A.

[0046] [Chemical Formula 2A]

[0047]

[0048] iPr can be represented by the following Chemical Formula 2B.

[0049] [Chemical formula 2B]

[0050]

[0051] iBu can be represented by the following chemical formula 2C.

[0052] [Chemical formula 2C]

[0053]

[0054] sBu can be represented by the following Chemical Formula 2D.

[0055] [Chemical Formula 2D]

[0056]

[0057] tBu can be represented by the following Chemical Formula 2E.

[0058] [Chemical formula 2E]

[0059]

[0060] In Chemical Formulae 2A to 2E, The symbol may mean a connection point with C of the nitrile group contained in one of No. 1 to No. 78 of the group A compounds.

[0061] The metal compound can be used as a deposition precursor. For example, the metal compound can be used as a deposition precursor for atomic layer deposition (ALD) or chemical vapor deposition (CVD). The metal compound can be used as a deposition precursor to form a metal-containing thin layer. The improvement of the stability of the deposition precursor can improve one or more characteristics of the deposited layer.

[0062] In some embodiments, the metal compound may include a metal (M) and a nitrile group (CN). Since the metal compound includes a nitrile group, the metal compound may have a low melting point. For example, the melting point of the metal compound may be in the range of -50°C to 60°C. The metal compound may be in a liquid state at room temperature (e.g., 25°C). Alternatively, the metal compound may be in a solid state at room temperature, but low energy may be required to provide the metal compound in a liquid state at room temperature. Therefore, it may be possible to easily transport the metal compound in a liquid state. In this case, since the metal compound according to some embodiments is used as a deposition precursor, a central supply system may be used to supply the deposition precursor. The central supply system may mean that the deposition precursor is supplied by a deposition system that will be referred to below. Figure 2 The precursor storage unit 30 is described as being supplied.

[0063] When the alkyl group is directly bonded to the metal of the deposition precursor, the deposition precursor may be unstable. For example, the metal deposition precursor may decompose before being introduced into the deposition chamber.

[0064] In some embodiments, the metal compound may include a nitrile group (CN). The nitrogen of the nitrile group may be directly bonded to the metal (M). The alkyl (R) may not be directly bonded to the metal (M), but may be bonded to the carbon of the nitrile group. Therefore, the metal compound of the present invention may have improved stability, such as compared to the stability of a metal compound with carbon directly bonded to a metal. For example, the metal compound may not decompose during transport and / or in the process of supplying the metal compound to a chamber.

[0065] During deposition, the nitrile group may be separated from the metal (M). In this case, the alkyl (R) may be separated from the metal together with the nitrile group. Therefore, the deposited layer may include the metal, but may not include elements derived from the nitrile group and / or the alkyl. The elements derived from the nitrile group or the alkyl may include, for example, one or more of: carbon, nitrogen and halogen elements. When the elements derived from the nitrile group or the alkyl remain on the deposited layer, the elements may act as impurities. When a thin layer is formed using a metal compound according to some embodiments as a deposition precursor, the thin layer may have a low amount of impurities. For example, the thin layer may include a metal, but does not include carbon. Therefore, the thin layer may have low resistivity and / or improved electrical properties.

[0066] When the metal compound is used as a deposition precursor, the deposition process may have a relatively wide deposition window. The deposition window may represent a temperature range in which the deposition process is performed when a certain deposition precursor is used. The deposition window may include an atomic layer deposition (ALD) window. Therefore, according to some embodiments of the present invention, it may be possible to reduce restrictions on deposition process conditions.

[0067] The metal compound may not include impurities or include impurities at a low concentration. The impurities may represent a material different from the material of Chemical Formula 1. The impurities may include one or more of the following: metal-containing impurities, halogen-containing impurities and / or organic impurities. The metal-containing impurities may include metal impurities. In some embodiments, the metal compound of the present invention may have a metal impurity concentration of less than 1ppm. The metal compound may have a metal impurity concentration in the range of 0ppb-100ppm, for example, 1ppb-100ppb. As used herein in this specification, the phrase "the concentration of a certain impurity is zero" may mean that impurities are not included. When the metal compound includes metal impurities containing a plurality of different metal elements, each of the metal elements may have a concentration of 100ppb or less, for example, 10ppb or less. The metal impurities may include one or more of alkali metals and / or alkaline earth metals. The halogen-containing impurities may include one or more of fluorine, chlorine, bromine and iodine. The concentration of halogen-containing impurities in the metal compound may be 100ppm or less. For example, the metal compound may have a concentration of halogen-containing impurities in an amount of 10ppm or less, for example, 1ppm or less. The concentration of organic impurities in the metal compound may be 500ppm or less. For example, the metal compound may have a concentration of organic impurities of 50ppm or less, such as 10ppm or less. The metal compound may not include moisture or include low concentrations of moisture. The concentration of moisture contained in the metal compound may be 10ppm or less, such as 1ppm or less. As used herein in this specification, the phrase "the concentration of moisture contained in a material is 10ppm or less" may mean that the concentration of moisture is in the range of 0-10ppm.

[0068] When the metal compound is in a liquid or solid state, the impurities may exist in the form of particles. The amount of impurity particles present in the metal compound may be low. The impurity particles may have a small diameter. When the diameter of the impurity particles is greater than 0.3 μm, 1 mL of the metal compound may contain 100 or less (e.g., 0-100) impurity particles with a diameter greater than 0.3 μm. When the diameter of the impurity particles is greater than 0.2 μm, 1 mL of the metal compound may contain 100 or less (e.g., 0-100) impurity particles with a diameter greater than 0.2 μm.

[0069] When the deposited precursor includes impurities, contaminated particles may form in and / or on the deposited thin layer. In some embodiments, the metal compound may not include impurities or include very low concentrations of impurities. Therefore, the deposited thin layer may exhibit superior properties.

[0070] The metal compound according to some embodiments may have a high vapor pressure and thus may be easily evaporated. When a deposition precursor including the metal compound of the present inventive concept is used, a deposition process may be easily performed.

[0071] An exemplary preparation of the metal compound is discussed below.

[0072] A metal halide and an alkyl nitrile may be added to a solvent, which may produce a mixture. The solvent may be an organic solvent such as hexane. The metal halide may include a metal and a halogen element bonded to the metal. The metal may be defined by M in Chemical Formula 1 and may include one selected from Nb and Ta. The halogen element may be one selected from F, Cl, Br and I. For example, the metal halide may include NbF 5 or TaF 5 . The alkyl nitrile may be a C3-C10 alkyl nitrile. Thereafter, the reaction of the mixture may be performed. The reaction may be performed, for example, at a temperature of about 50° C. Thereafter, the solvent and residual reactants may be removed so that the product may be separated. The product may be subjected to distillation and / or purification to produce the metal compound. The metal compound may be produced according to a variety of methods, without limitation thereto.

[0073] A deposition process using a metal compound according to the present inventive concept and a method of forming a thin layer according to some embodiments of the present inventive concept will be discussed below.

[0074] Figure 1 A flow chart showing a deposition process using a metal compound according to some example embodiments is illustrated. Figure 2 The illustration shows a schematic diagram of a deposition system according to some example embodiments.

[0075] Reference Figure 1 The deposition process may include preparing a deposition precursor including a metal compound (S10), supplying the deposition precursor to form a precursor layer (S20), and supplying a reaction gas to form a thin layer (S30). The deposition process may further include performing a first exhaust process (S21) and / or performing a second exhaust process (S31). The deposition process may be an atomic layer deposition process.

[0076] Reference Figure 1 and 2 , the deposition system 10 may include a chamber 50, a precursor supply unit 20, a precursor storage unit 30, and a reaction gas supply unit 40. The deposition system 10 may be used in an atomic layer deposition process. Alternatively, the deposition system 10 may be used in a chemical vapor deposition process. A substrate (base plate) 1000 may be loaded into the chamber 50. The substrate 1000 may be a wafer substrate such as a semiconductor wafer.

[0077] The reaction gas may be present or provided in the reaction gas supply unit 40 . The reaction gas may include one or more of the following: an oxidizing gas, a reducing gas, and / or a nitrogen-containing gas. The reaction gas supply unit 40 may supply the reaction gas to the chamber 50 .

[0078] The precursor storage unit 30 may include, for example, a storage tank. The tank may include or be provided with a deposition precursor in a liquid state. The first supply pipe 31 may connect the precursor storage unit 30 to the precursor supply unit 20. Therefore, it may be possible to omit the step of providing a separate tank to the precursor supply unit 20 and the step of replacing the precursor storage tank 30. The precursor storage unit 30 may be used to supply the deposition precursor. The deposition system 10 may be a central supply system.

[0079] A deposition precursor including the metal compound may be prepared (S10). The deposition precursor may be provided to a precursor storage unit 30. The deposition precursor in the precursor storage unit 30 may be transported to the precursor supply unit 20 via a first supply pipe 31. When the deposition precursor is in a solid state, it may be difficult for the deposition precursor to flow through the first supply pipe 31. As discussed above, since the metal compound according to some embodiments has a low melting point, the metal compound may be in a liquid state at room temperature. Alternatively, the metal compound may be in a solid state at room temperature, but low energy may be required to convert the metal compound into a liquid state at room temperature. Since the deposition precursor includes the metal compound according to some embodiments, the deposition precursor may be easily transported via the first supply pipe 31.

[0080] In another example, the metal compound can be dissolved in an organic solvent, and thus a precursor solution can be manufactured. The organic solvent may include one or more of the following: an acetate solvent, an ether solvent, a ketone solvent, a hydrocarbon solvent and / or a heteroaromatic solvent. The concentration of moisture in the organic solvent may be 10ppm or less, for example, 1ppm or less. The acetate solvent may include one or more of the following: ethyl acetate, butyl acetate and methoxyethyl acetate. The ether solvent may include one or more of the following: tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether and dioxane. The ketone solvent may include, for example, methyl butyl ketone. The hydrocarbon solvent may include a cyano group. The hydrocarbon solvent including a cyano group may include one or more of the following: 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane and 1,4-dicyanobenzene. The heteroaromatic solvent may include one or more of pyridine and lutidine (dimethylpyridine).

[0081] When the deposition precursor is provided in the form of a precursor solution, the deposition precursor may have a molar concentration of 0.01 mol / L to 2.0 mol / L, for example, 0.05 mol / L to 1.0 mol / L.

[0082] In addition to the metal compound, the deposition precursor may further include another precursor. The metal compound and the other precursor may be mixed with each other to make a mixed precursor. For example, in some embodiments, the deposition precursor may be a mixed precursor. The mixed precursor may be provided to the chamber 50. In some embodiments, the other precursor may be provided to the chamber 50 through a separate supply channel independently of the metal compound. The other precursor may have stability. For example, the other precursor may not react with the metal compound or may have extremely low reactivity with the metal compound. Therefore, decomposition and / or oxidation of the other precursor, decomposition and / or oxidation of the metal compound, and / or reaction between the other precursor and the metal compound may not occur. The concentration of moisture in the other precursor may be 10ppm or less, for example 1ppm or less.

[0083] The additional precursors may include one or more of the following: semiconductor compounds, metal compounds, and / or organic compounds. The semiconductor compounds may include one or more of silicon and germanium. The metal compounds may include one or more of the following: lithium, sodium, potassium, magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, rhodium, iridium, nickel, palladium, platinum, silver, copper, gold, zinc, aluminum, gallium, indium, tin, lead, antimony, bismuth, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and ruthenium.

[0084] The organic compound may include one or more of the following: an alcohol compound, a diol compound, a β-diketone compound, a cyclopentadiene compound, and / or an amine compound. The organic compound may be used to provide an organic ligand. For example, the deposited thin layer may include a ligand derived from the organic compound.

[0085] The alcohol compound may include, for example, one or more of the following: an alkyl alcohol compound, an ether alcohol compound, and / or a dialkylamino alkyl alcohol compound. The alkyl alcohol compound may be an alcohol compound including an alkyl group. For example, the alkyl alcohol compound may include one or more of the following: ethanol, propanol, isopropanol, butanol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, amyl alcohol, isopentanol, and tert-amyl alcohol. The ether alcohol compound may be an alcohol compound including an ether group. For example, the ether alcohol compound may include one or more of the following: 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. The dialkylaminoalkyl alcohol compound may include, for example, one or more of the following: 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.

[0086] The diol compound may include, for example, one or more of 1,2-ethanediol, 1,2-propylene glycol, 1,3-propylene glycol, 2,4-hexanediol, 2,2-dimethyl-1,3-propylene glycol, 2,2-diethyl-1,3-propylene glycol, 1,3-butylene glycol, 2,4-butylene glycol, 2,2-diethyl-1,3-butylene glycol, 2-ethyl-2-butyl-1,3-propylene glycol, 2,4-pentanediol, 2-methyl-1,3-propylene glycol, 2-methyl-2,4-pentanediol, and 2,4-dimethyl-2,4-pentanediol.

[0087] The β-diketone compound may include one or more of the following: an alkyl-substituted β-diketone compound, a fluorine-substituted β-diketone compound, and an ether-substituted β-diketone compound. The alkyl-substituted β-diketone compound may include one or more of the following: 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-dimethylnonane-4,6-dione, 2-methyl-6-ethyldecane-3,5-dione, and 2,2-dimethyl-6-ethyldecane-3,5-dione. The fluorine-substituted β-diketone compound may include one or more of the following: 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. The ether-substituted β-diketone compound may include one or more of 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.

[0088] The cyclopentadiene compound may include one or more of cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, sec-butylcyclopentadiene, isobutylcyclopentadiene, tert-butylcyclopentadiene, dimethylcyclopentadiene, and tetramethylcyclopentadiene.

[0089] The amine compound may include one or more of methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, ethylmethylamine, propylmethylamine, and isopropylmethylamine.

[0090] The deposition precursor may further include a nucleophile. The nucleophile may improve the stability of the deposition precursor. For example, the nucleophile may improve the stability of the metal compound of the present invention and / or the additional precursor. The nucleophile may be present in an amount in the range of 0.1 mol to 10 mol, such as 1 mol to 4 mol, per 1 mol of the deposition precursor. The concentration of water in the nucleophile may be 10 ppm or less, such as 1 ppm or less.

[0091] The nucleophilic reagent may include one or more of the following: glycol ether reagents, crown ether reagents, polyamine reagents, heterocyclic reagents, β-ketoester reagents, and β-diketone reagents. The glycol ether reagent may include, for example, one or more of the following: glycol dimethyl ether, diglycol dimethyl ether, triglycol dimethyl ether, and tetraglycol dimethyl ether. The crown ether reagent may include one or more of the following: 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8, and dibenzo-24-crown-8.

[0092] The polyamine reagent may include multiple amino groups. For example, the polyamine reagent may include one or more of the following: ethylenediamine, N,N,N',N'-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,1,4,7,7-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, and triethoxytriethylenetetramine. The polyamine reagent may include cyclic polyamine reagents. The cyclic polyamine reagent may include, for example, one or more of cyclam and cyclen.

[0093] The heterocyclic reagent may include one or more of the following: pyridine, pyrrolidine, piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, azoles, thiazoles, and oxathioranes.

[0094] The β-ketoester reagent may include, for example, one or more of acetoacetate, methyl acetoacetate, ethyl acetoacetate, and 2-methoxyethyl acetoacetate.

[0095] The β-diketone reagent may include, for example, one or more of acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, and dipivaloylmethane.

[0096] The second supply pipe 21 may connect the precursor supply unit 20 to the chamber 50. The metal compound according to some embodiments may have high vapor pressure and high volatility, and thus may easily form a gaseous deposition precursor. The gaseous deposition precursor may be effortlessly supplied from the precursor supply unit 20 to the chamber 50 through the second supply pipe 21.

[0097] In some embodiments, a gas transport method may be used to supply the deposition precursor to the chamber 50. For example, a liquid deposition precursor may be heated and / or depressurized in the precursor supply unit 20, which may result in evaporation of the deposition precursor. In other embodiments, a liquid transport method may be used to supply the deposition precursor to the chamber 50. For example, an evaporation chamber (not shown) may be provided separately between the precursor supply unit 20 and the chamber 50. In this case, a second supply pipe 21 may connect the evaporation chamber to the chamber 50. The deposition precursor in a liquid state may be supplied to the evaporation chamber. The deposition precursor may be heated and / or depressurized in the evaporation chamber, which may result in evaporation of the deposition precursor. Thus, a gaseous deposition precursor may be formed. The gaseous deposition precursor may be supplied to the chamber 50 alone or together with a carrier gas. The carrier gas may include an inert gas such as argon, nitrogen, and / or helium.

[0098] The deposition precursor may be evaporated at a temperature of about 0° C. to about 150° C. The evaporation of the deposition precursor may be performed at a pressure of about 1 Pa to about 10,000 Pa. Figure 3A-3B The formation of a thin layer using the metal compound according to some embodiments of the present inventive concept as a deposition precursor is discussed in detail.

[0099] Figure 3A and 3B A cross-sectional view illustrating a method of forming a thin layer according to some example embodiments is illustrated.

[0100] Reference Figure 1 , 2 3A, a deposition precursor 2001 may be provided to the chamber 50 to form a precursor layer 2100 on the substrate 1000 (S20). The chamber 50 may receive the deposition precursor 2001 in a gaseous state. The deposition precursor 2001 may include a metal compound as described herein.

[0101] The substrate 1000 may include, for example, a semiconductor material. For example, the substrate 1000 may include one or more of silicon, germanium, silicon nitride, titanium nitride, tantalum nitride, titanium oxide, niobium oxide, zirconium oxide, hafnium oxide, and lanthanum oxide. The substrate 1000 may have one or more of a plate shape, a spherical shape, a fiber shape, and a scale shape. Although not shown, a groove may be provided and / or formed on the substrate 1000.

[0102] During the step S20 of supplying the deposition precursor 2001, the substrate 1000 may be maintained at and / or exposed to a temperature of 150° C.-400° C., for example, 200° C.-300° C. During the step S20 of supplying the deposition precursor 2001, the chamber 50 may have a pressure of 1 Pa-10,000 Pa, for example, 10 Pa-1,000 Pa. During the step S20 of supplying the deposition precursor 2001, light and / or heat may be applied to the chamber 50. In this case, the pressure of the chamber 50 may range from 10 Pa to 1,013 Pa. During the step S20 of supplying the deposition precursor 2001 into the chamber 50, plasma may be applied to the chamber 50. In this case, the pressure of the chamber 50 may range from 10 Pa to 2,000 Pa.

[0103] The deposition precursor 2001 may be adsorbed onto the top surface 1000a of the substrate 1000, thereby forming a precursor layer 2100. When the metal compound of Chemical Formula 1 is used as the deposition precursor 2001, the nitrile group of the metal compound may be separated from the metal (M) during and / or before the adsorption of the deposition precursor 2001. In this case, the alkyl group (R) may be separated from the metal together with the nitrile group. Thereafter, one or more halogen elements contained in the metal compound may be further separated from the metal (M). The halogen element may be, for example, X in Chemical Formula 1. 1 , X 2 , X 3 , X 4 , and X 5 Thus, after the formation of the precursor layer 2100 is completed, the precursor layer 2100 may not include the nitrile group, the alkyl group, and / or an element derived from the nitrile group and / or the alkyl group. For example, the precursor layer 2100 may include a metal, but does not include carbon and / or a halogen element.

[0104] In some embodiments, after step S20 of forming the precursor layer 2100, a first exhaust process (S21) may be performed. During the first exhaust process, the residual deposition precursor 2001 (e.g., the deposition precursor remaining in the chamber 50 that is not adsorbed on the top surface 1000a of the substrate 1000) and the byproduct gas may be removed from the chamber 50. The first exhaust process may include a purge process, a decompression process, or a combination thereof. The purge process may be performed in a manner of supplying an inert gas to the chamber 50. The inert gas may include one or more of the following: argon, nitrogen, and helium. The decompression process may include reducing the pressure of the chamber 50. The decompression process may continue until the pressure of the chamber 50 is close to 0.01Pa-300Pa, for example, 0.01Pa-100Pa.

[0105] like Figure 1 , 2As shown in FIG. 3B , a reaction gas may be supplied to the chamber 50 to form a thin layer 2000 (S30). The reaction gas may react with the precursor layer 2100. For example, the reaction gas may react with the deposition precursor 2001 adsorbed on the substrate 1000. Thus, a thin layer 2000 may be formed on the substrate 1000. In some embodiments, the thin layer may have a thickness of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 nm or more.

[0106] The reaction gas may include one or more of the following: an oxidizing gas, a reducing gas, and / or a nitrogen-containing gas. The oxidizing gas may include, for example, one or more of the following: oxygen, ozone, nitrogen dioxide, nitric oxide, water vapor, hydrogen peroxide, acetic acid, and acetic anhydride. The reducing gas may include hydrogen. The nitrogen-containing gas may include one or more of the following: ammonia, hydrazine, methylhydrazine, monoalkylamines, dialkylamines, trialkylamines, triamines, and alkylenediamines. In some embodiments, the reaction gas may include NO 2 (nitrogen dioxide), N 2 O (nitrous oxide), alcohol, NOx, COx, SOx, CO 2 , H 2 O 2 , HCOOH, CH 3 COOH, and / or (CH 3 CO) 2 O, wherein x is a positive real number. The reaction gas may be a mixed gas including two or more different gases. In some embodiments, the mixed gas may include ammonia.

[0107] When a nitrogen-containing gas is used as the reaction gas, the deposited thin layer 2000 may include a metal nitride layer or a metal-containing composite nitride layer. When an oxidizing gas is used as the reaction gas, the deposited thin layer 2000 may include oxygen. For example, the deposited thin layer 2000 may include a metal oxide layer or a metal-containing composite oxide layer.

[0108] During the step S30 of supplying the reaction gas to form the thin layer 2000, the substrate 1000 may be maintained and / or exposed to a temperature of 25°C-400°C, for example, 200°C-350°C. During the step S30 of supplying the reaction gas to form the thin layer 2000, the chamber 50 may have a pressure of 1Pa-10,000Pa, for example, 10Pa-1,000Pa. During the step S30 of supplying the reaction gas to form the thin layer 2000, light and / or heat may be applied to the chamber 50. In this case, the pressure of the chamber 50 may range from 10Pa-1,013Pa. During the step S30 of supplying the reaction gas to form the thin layer 2000, plasma may be applied to the chamber 50. In this case, the pressure of the chamber 50 may range from 10Pa-2,000Pa.

[0109] The metal compound according to some embodiments of the present inventive concept may have high reactivity with nitrogen-containing gas. When the precursor layer 2100 is formed using the metal compound according to some embodiments, the precursor layer 2100 may have high reactivity with nitrogen-containing gas. Therefore, it may be possible to easily form a metal nitride layer or a metal-containing composite nitride layer. The thin layer 2000 may exhibit improved characteristics and / or have a low amount of impurities.

[0110] In the deposition process, energy may be additionally supplied to the chamber 50. The energy may include one or more of the following: plasma, light, heat, and voltage. For example, the deposition process may be completed by performing atomic layer deposition. The supply of energy may be performed in one or more of the following: step S20 of supplying a deposition precursor 2001, step S21 of performing a first exhaust process, step S30 of supplying a reaction gas, and step S31 of performing a second exhaust process. In some embodiments, the deposition process may be performed by performing one of thermal chemical vapor deposition (CVD), plasma CVD, optical CVD, and optical-plasma CVD.

[0111] According to some embodiments, the material of the thin layer 2000 may be determined by the type of the metal compound, the type of the reaction gas, and the type of the additional precursor. The thin layer 2000 may include a metal-containing layer. The metal-containing layer may include a niobium-containing layer or a tantalum-containing layer. The niobium-containing layer may include, for example, one or more of the following: a niobium layer, a niobium alloy layer, a niobium nitride layer, a niobium oxide layer, and / or a niobium composite oxide layer. The niobium composite oxide layer may include one or more of the following: a niobium oxynitride layer, a niobium metal oxide layer, and / or a niobium carbonyl layer. The niobium alloy layer may include niobium and a metal other than niobium. For example, the niobium alloy layer may include an alloy of Nb-Hf or Nb-Ti. The niobium metal oxide layer may be an oxide layer of niobium and a metal other than niobium. The tantalum-containing layer may include, for example, one or more of the following: a tantalum layer, a tantalum alloy layer, a tantalum nitride layer, a tantalum oxide layer, and a tantalum composite oxide layer. The tantalum composite oxide layer may include one or more of the following: a tantalum oxynitride layer, a tantalum metal oxide layer, and a tantalum carbonyl layer. The tantalum alloy layer may include tantalum and a metal other than tantalum. The tantalum alloy layer may include, for example, an alloy of Ta—Ti or Ta—W. The niobium or tantalum-containing layer according to some embodiments may have improved electrical and optical properties.

[0112] The deposition rate of the precursor layer 2100 can be adjusted by the supply conditions of the deposition precursor 2001, the temperature of the substrate 1000, and / or the pressure of the chamber 50. The supply conditions of the deposition precursor 2001 may include the evaporation temperature of the deposition precursor 2001 and / or the pressure of the evaporated deposition precursor 2001. When the precursor layer 2100 is formed at an extremely low rate (e.g., less than 0.01 nm / minute), the thin layer 2000 may have a low productivity. When the precursor layer 2100 is deposited at an extremely high rate (e.g., greater than 100 nm / minute), the thin layer 2000 may have poor characteristics. According to some embodiments, the precursor layer 2100 may be deposited at a rate of 0.05 nm / minute-100 nm / minute, for example, 1 nm / minute-50 nm / minute. As a result, the thin layer 2000 may exhibit excellent characteristics and / or have an improved productivity.

[0113] After the thin layer 2000 is formed, an annealing process may be further performed on the thin layer 2000. The annealing process may be performed in an inert gas environment, an oxidizing gas environment, or a reducing gas environment. The annealing process may improve the electrical properties of the thin layer 2000. Here, the electrical properties may include dielectric properties.

[0114] After the thin layer 2000 is formed, a reflow process may be further performed on the thin layer 2000. The reflow process may improve the step coverage of the thin layer 2000. The reflow process may be performed at a temperature of, for example, 200°C-1000°C, for example, 250°C-500°C.

[0115] After forming the thin layer 2000, a second exhaust process (S31) may be performed. During the second exhaust process, residual reaction gas and / or byproduct gas may be removed from the chamber 50. Similar to the first exhaust process, the second exhaust process may include a purge process, a decompression process, or a combination thereof.

[0116] In some embodiments, after step S20 of supplying the deposition precursor 2001, step S30 may be performed to supply the reaction gas. In other embodiments, step S30 of supplying the reaction gas may be performed simultaneously with step S20 of supplying the deposition precursor 2001. In this case, it may be possible to omit the first exhaust process (e.g., the purge process).

[0117] A single cycle (period) may be composed of the following: step S20 of supplying the deposition precursor 2001, step S21 of performing the first exhaust process, step S30 of supplying the reaction gas, and step S31 of performing the second exhaust process. The formation process of the thin layer 2000 may be performed several times. For example, the cycle for forming the thin layer 2000 may be repeated. In this case, the thin layer 2000 may include a plurality of stacked thin layers. Therefore, the total thickness of the thin layer 2000 may be controlled.

[0118] In some embodiments, the thin layer 2000 may be used as an electrode of a memory device, a resistance layer, an antimagnetic layer of a hard disk, or a catalyst of a polymer electrolyte membrane fuel cell. The thin layer 2000 is not limited thereto but may be used as a component of various devices.

[0119] The preparation of metal compounds and the formation of thin layers using the same will be discussed below with reference to Experimental Examples and Comparative Examples.

[0120] Inductively coupled plasma atomic emission spectrometer (ICP-AES) was used for elemental analysis in the following Experimental Examples and Comparative Examples.

[0121] In the following experimental examples and comparative examples, benzene substituted with deuterium was used as a solvent for nuclear magnetic resonance spectroscopy. The results of nuclear magnetic resonance spectroscopy are expressed by chemical shift (number of H, multiplicity).

[0122] In the following experimental examples and comparative examples, a thermogravimetric-differential thermal analysis (TG-DTA) device was used to perform thermal analysis. In this case, argon was supplied at 100 mL / min. The heating rate was 10° C. / min. The differential thermal analysis was performed at a pressure of 760 Torr. When the mass of the sample supplied to the device was reduced to 50% by weight of the initial supply mass of the sample, the temperature (hereinafter referred to as the 50% by weight reduction temperature) was measured.

[0123] In the following experimental examples and comparative examples, the results of elemental analysis are expressed by measured values. In addition, theoretical values ​​are calculated and shown together with the measured values.

[0124] 1. Manufacture of metal compounds

[0125] <Experimental Example 1> Production of the Metal Compound Represented by No. 4

[0126] Under argon atmosphere, 20.0 g (0.106 mol) of NbF 5 and 300 ml of dehydrated hexane are added to a 500 mL beaker. At room temperature (e.g., 25° C.), a mixed solution is formed by adding 44.2 g (0.532 moles) of isovaleronitrile to the beaker. The mixed solution is stirred at 50° C. for 5 hours. Thereafter, the solvent is removed from the mixed solution at 50° C. under reduced pressure. The NbF remaining after the reaction is removed from the beaker whose temperature is raised to 90° C. 5 and isovaleronitrile, which produces a preliminary product. The preliminary product is an orange liquid. The preliminary product is distilled at a temperature of 120° C. under a pressure of 30 Pa to obtain the final product, or the metal compound represented by No. 4. The metal compound of No. 4 is a white solid.

[0127] [Yield]

[0128] The final product obtained (metal compound No. 4) had a mass of 11.2 g. The yield was calculated to be 38.9%.

[0129] [Thermal Analysis_TG-DTA]

[0130] The 50 wt% reduction temperature was measured to be 205°C.

[0131] [Nuclear Magnetic Resonance (1H-NMR) Analysis]

[0132] 0.84ppm(1H, multiplet),0.74ppm(2H, doublet),0.22ppm(6H, doublet)

[0133] [Elemental analysis]

[0134] Nb: measured value: 34.5% (theoretical value: 34.3%)

[0135] C: measured value: 22.5% (theoretical value: 22.2%)

[0136] H: measured value: 2.9% (theoretical value: 3.3%)

[0137] N: measured value; 4.9% (theoretical value; 5.2%)

[0138] F: measured value: 35.2% (theoretical value: 35.0%)

[0139] <Experimental Example 2> Production of the Metal Compound Represented by No. 5

[0140] Under argon atmosphere, 20.0 g (0.106 mol) of NbF 5 and 300 ml of dehydrated hexane are added to a 500 mL beaker. At room temperature (e.g., 25° C.), a mixed solution is formed by adding 44.2 g (0.532 moles) of 2-methylbutyronitrile to the beaker. The mixed solution is stirred at 50° C. for 5 hours. Thereafter, the solvent is removed from the mixed solution at 50° C. under reduced pressure. The NbF remaining after the reaction is removed from the beaker whose temperature is raised to 90° C. 5 and 2-methylbutyronitrile, which produces a preliminary product. The preliminary product is an orange liquid. The preliminary product is distilled at a temperature of 110° C. under a pressure of 30 Pa to obtain the final product, or the metal compound represented by No. 5. The metal compound of No. 5 is a colorless transparent liquid compound.

[0141] [Yield]

[0142] The final product obtained (metal compound No. 5) had a mass of 14.5 g. The yield was calculated to be 50.4%.

[0143] [Thermal Analysis_TG-DTA]

[0144] The 50 wt% reduction temperature was found to be 200°C.

[0145] [Nuclear Magnetic Resonance (1H-NMR) Analysis]

[0146] 1.22ppm(1H, multiplet),0.50ppm(2H, doublet),0.30ppm(3H, doublet),0.19ppm(3H, triplet)

[0147] [Elemental analysis]

[0148] Nb: measured value: 34.4% (theoretical value: 34.3%)

[0149] C: measured value: 22.6% (theoretical value: 22.2%)

[0150] H: measured value; 3.1% (theoretical value; 3.3%)

[0151] N: measured value; 5.0% (theoretical value; 5.2%)

[0152] F: measured value: 34.9% (theoretical value: 35.0%)

[0153] <Experimental Example 3> Production of the Metal Compound Represented by No. 9

[0154] Under argon atmosphere, 20.0 g (0.106 mol) of NbF 5 and 300 ml of dehydrated hexane are added to a 500 mL beaker. At room temperature (e.g., 25° C.), a mixed solution is formed by adding 66.6 g (0.532 moles) of n-octanonitrile to the beaker. The mixed solution is stirred at 50° C. for 5 hours. Thereafter, the solvent is removed from the mixed solution at 50° C. under reduced pressure. The NbF remaining after the reaction is removed from the beaker whose temperature is raised to 120° C. 5 and n-octanonitrile, which produces a preliminary product. The preliminary product is an orange liquid. The preliminary product is distilled at a temperature of 150° C. under a pressure of 30 Pa to obtain the final product, or the metal compound represented by No. 9. The metal compound of No. 9 is a white solid.

[0155] [Yield]

[0156] The final product obtained (metal compound No. 9) had a mass of 13.6 g. The yield was calculated to be 41.1%.

[0157] [Thermal Analysis_TG-DTA]

[0158] The 50 wt% reduction temperature was measured to be 230°C.

[0159] [Nuclear Magnetic Resonance (1H-NMR) Analysis]

[0160] 1.12ppm(2H, multiplet),0.92ppm(2H, multiplet),0.83ppm(3H, triplet),0.78ppm(2H, multiplet),0.71ppm(2H, multiplet),0.55ppm(2H, multiplet),0.44ppm(2H, multiplet)

[0161] [Elemental analysis]

[0162] Nb: measured value: 29.8% (theoretical value: 29.7%)

[0163] C: measured value: 30.9% (theoretical value: 30.7%)

[0164] H: measured value; 4.5% (theoretical value; 4.8%)

[0165] N: measured value; 4.4% (theoretical value; 4.5%)

[0166] F: measured value: 30.4% (theoretical value: 30.3%)

[0167] <Experimental Example 4> Production of the Metal Compound Represented by No. 11

[0168] Under argon atmosphere, 20.0 g (0.106 mol) of NbF 5 and 300 ml of dehydrated hexane are added to a 500 mL beaker. At room temperature (e.g., 25° C.), a mixed solution is formed by adding 81.5 g (0.532 moles) of n-decane nitrile to the beaker. The mixed solution is stirred at 50° C. for 5 hours. Thereafter, the solvent is removed from the mixed solution at 50° C. under reduced pressure. The NbF remaining after the reaction is removed from the beaker whose temperature is raised to 120° C. 5 and n-decane nitrile, which produces a preliminary product. The preliminary product is an orange liquid. The preliminary product is distilled at a temperature of 160° C. under a pressure of 30 Pa to obtain the final product, or the metal compound represented by No. 11. The metal compound of No. 11 is a white solid.

[0169] [Yield]

[0170] The final product obtained (metal compound No. 11) had a mass of 13.9 g. The yield was calculated to be 38.5%.

[0171] [Thermal Analysis_TG-DTA]

[0172] The 50 wt% reduction temperature was measured to be 235°C.

[0173] [Nuclear Magnetic Resonance (1H-NMR) Analysis]

[0174] 1.29ppm(2H, multiplet),1.21ppm(2H, multiplet),1.19ppm(2H, multiplet),0.97ppm(2H, multiplet),0.93ppm(3H, triplet),0.77ppm(2H, multiplet),0.72ppm(2H, multiplet),0.57ppm(2H, multiplet),0.45ppm(2H, multiplet)

[0175] [Elemental analysis]

[0176] Nb: measured value: 27.3% (theoretical value: 27.2%)

[0177] C: measured value: 35.4% (theoretical value: 35.2%)

[0178] H: measured value; 5.3% (theoretical value; 5.6%)

[0179] N: measured value; 4.0% (theoretical value; 4.1%)

[0180] F: measured value: 28.0% (theoretical value: 27.9%)

[0181] <Experimental Example 5> Production of the Metal Compound Represented by No. 45

[0182] Under argon atmosphere, 20.0 g (0.074 mol) of NbCl 5 (V) and 300ml of dehydrated toluene are added to a 500mL 4-necked flask. At room temperature (e.g., 25°C), a mixed solution is formed by adding 9.27g (0.074 mol) of n-octanonitrile to the beaker. The mixed solution is stirred in a bath for 5 hours. The bath is maintained at a temperature of 50°C. At a temperature of 50°C, the mixed solution undergoes a decompression process to remove the solvent from the mixed solution. Thus, a preliminary product is obtained. At a pressure of 30Pa at a temperature of 180°C, the preliminary product is distilled to obtain the final product, or the metal compound represented by No.45. The final product is a yellow solid.

[0183] [Yield]

[0184] The final product obtained (metal compound No. 45) had a mass of 21.9 g. The yield was calculated to be 75.0%.

[0185] [Thermal Analysis_TG-DTA]

[0186] The 50 wt% reduction temperature was measured to be 244°C.

[0187] [Nuclear Magnetic Resonance (1H-NMR) Analysis]

[0188] 2.79ppm(2H, triplet),1.88ppm(2H, quintet),1.55ppm(2H, quintet),1.36ppm(6H, multiplet),0.90ppm(3H, triplet)

[0189] [Elemental analysis]

[0190] Nb: measured value: 23.7% (theoretical value: 23.5%)

[0191] C: measured value: 24.9% (theoretical value: 24.3%)

[0192] H: measured value; 4.1% (theoretical value; 3.8%)

[0193] N: measured value; 3.6% (theoretical value; 3.5%)

[0194] Cl: measured value: 44.5% (theoretical value: 44.8%)

[0195] <Experimental Example 6> Production of the Metal Compound Represented by No. 41

[0196] Under argon atmosphere, 20.0 g (0.074 mol) of NbCl 5 (V) and 300ml of dehydrated toluene are added to a 500mL 4-necked flask. At room temperature (e.g., 25°C), a mixed solution is formed by adding 6.16g (0.074 mol) of sec-butyl cyanide to the beaker. The mixed solution is stirred in a bath for 5 hours. The bath is maintained at a temperature of 50°C. At a temperature of 50°C, the mixed solution undergoes a decompression process to remove the solvent from the mixed solution. Thus, a preliminary product is obtained. At a pressure of 30Pa at a temperature of 150°C, the preliminary product is distilled to obtain the final product, or the metal compound represented by No.41. The final product is a yellow solid.

[0197] [Yield]

[0198] The final product obtained (metal compound No. 41) had a mass of 20.8 g. The yield was calculated to be 79.5%.

[0199] [Thermal Analysis_TG-DTA]

[0200] The 50 wt% reduction temperature was found to be 223°C.

[0201] [Nuclear Magnetic Resonance (1H-NMR) Analysis]

[0202] 1.27ppm(1H, sextet), 0.64ppm(2H, multiplet), 0.44ppm(3H, triplet), 0.25ppm(3H, doublet)

[0203] [Elemental analysis]

[0204] Nb: measured value: 26.9% (theoretical value: 26.3%)

[0205] C: measured value: 17.6% (theoretical value: 17.0%)

[0206] H: measured value: 2.8% (theoretical value: 2.6%)

[0207] N: measured value; 4.0% (theoretical value; 4.1%)

[0208] Cl: measured value: 50.8% (theoretical value: 50.2%)

[0209] <Comparative Example 1>

[0210] A metal compound represented by Chemical Formula 3A was prepared as a comparative example.

[0211] [Chemical formula 3A]

[0212]

[0213] In Chemical Formula 3A, Me is a methyl group.

[0214] <Comparative Example 2>

[0215] A metal compound represented by Chemical Formula 3B was prepared as a comparative example.

[0216] [Chemical formula 3B]

[0217]

[0218] In Chemical Formula 3B, Et is an ethyl group.

[0219] 2. Formation of thin layer

[0220] The thin layer was formed by using an atomic deposition device. The formation of the thin layer included performing a cycle including the following process 1, process 2, process 3, and process 4, and repeating the cycle 150 times. In this case, the substrate was at a temperature of 250° C. Ammonia gas was used as a reaction gas.

[0221] Process 1: The precursor supply unit was heated to 90°C and adjusted to a pressure of 100 Pa, which resulted in evaporation of the deposition precursor. The deposition precursor vapor was supplied to the chamber for 30 seconds. The deposition precursor vapor was supplied with a pressure of 100 Pa.

[0222] Process 2: Argon gas was supplied to purge the chamber for 10 seconds.

[0223] Process 3: Reaction gas was supplied to the chamber at a pressure of 100 Pa for 30 seconds.

[0224] Process 4: Argon gas was supplied to purge the chamber for 10 seconds.

[0225] Each of the metal compounds of Experimental Examples 1, 2, 3, and 4 and Comparative Examples 1 and 2 was used as a deposition precursor for forming the thin layer.

[0226] 3. Evaluation of thin layers

[0227] X-ray reflectivity was used to measure the thickness of the thin layer.

[0228] X-ray diffraction was used to ascertain the presence of compounds in the thin layers.

[0229] X-ray photoelectron spectroscopy was used to measure the amount of carbon contained in the thin layer.

[0230] Table 1 lists the thermal analysis results of the metal compounds produced by Experimental Examples 1 to 4. When the mass of a sample supplied to a thermogravimetric-differential thermal analysis (TG-DTA) apparatus decreased to 50 wt % of the initial supplied mass of the sample, the temperature (hereinafter referred to as TG50) was measured.

[0231] [Table 1]

[0232]

[0233] Referring to Table 1, it is observed that the TG50 of Experimental Examples 1-4 is 250°C or less, for example, 100°C-250°C. The lower the TG50, the higher the vapor pressure of the compound. It can be determined that the metal compounds of Experimental Examples 1-4 have high vapor pressures. In particular, it is observed that the metal compounds of Experimental Examples 1 and 2 each have a low TG50. From these results, it can be found that the metal compounds of Experimental Examples 1 and 2 have extremely high vapor pressures.

[0234] Table 2 shows the melting points measured in Experimental Examples 1-4 and Comparative Examples 1 and 2.

[0235] [Table 2]

[0236]

[0237]

[0238] Referring to Table 2, the metal compounds of Experimental Examples 1-4 have a melting point lower than that of the metal compounds of Comparative Examples 1 and 2. In particular, the metal compound of Experimental Example 2 has an extremely low melting point. The metal compounds of Comparative Examples 1 and 2 each have a melting point of 130°C or higher. When the metal compound of Comparative Example 1 or 2 is used as a deposition precursor, it may be difficult to transport the deposition precursor. The metal compounds of Experimental Examples 1-4 may have a relatively low melting point (e.g., 60°C or lower). The deposition precursor may be transported in a liquid state. The lower the melting point of the deposition precursor, the easier it may be to transport the deposition precursor. Therefore, when the metal compounds of Experimental Examples 1-4 are used as deposition precursors, it may be easy to transport the deposition precursor, especially when compared with Comparative Examples 1 and 2.

[0239] Table 3 lists the thickness and carbon amount of thin layers deposited using the metal compounds of Experimental Examples 1 to 4 or Comparative Examples 1 and 2. For such thin layers, 0.1 atomic mass % was given as the minimum detection limit of the amount of carbon in the thin layer.

[0240] [Table 3]

[0241] Thickness of thin layer (nm) Amount of carbon in the thin layer Experimental Example 1 8 Not Detected Experimental Example 2 10 Not Detected Experimental Example 3 6 Not Detected Experimental Example 4 6 Not Detected Comparative Example 1 2 6 atomic mass% Comparative Example 2 3 4 atomic mass%

[0242] Referring to Table 3, although the thin layers of Experimental Examples 1 to 4 have a thickness greater than that of the thin layers of Comparative Examples 1 and 2, the thin layers of Experimental Examples 1 to 4 have a carbon amount less than that of the thin layers of Comparative Examples 1 and 2. Carbon was not detected in the thin layers of Experimental Examples 1 to 4. In particular, although the thin layer of Experimental Example 2 had a thickness of 10 nm, carbon was not detected in the thin layer of Experimental Example 2. It can be found that impurities are not included or are included in extremely small amounts in the thin layers of Experimental Examples 1 to 4.

[0243] Figures 4A-4G 1 and 2. A cross-sectional view illustrating a method of manufacturing a semiconductor device according to some example embodiments of the present inventive concept is illustrated. Repeated descriptions will be omitted hereinafter.

[0244] Reference Figure 4A , an interlayer dielectric layer 110 may be formed on the top surface of the substrate 1000. The substrate 1000 may be formed as described above. Figure 3A and 3B The above discussion is substantially the same as that in . For example, the substrate 1000 may be a semiconductor substrate. The interlayer dielectric layer 110 may include one or more of the following: a silicon oxide layer, a silicon nitride layer, and a silicon oxynitride layer.

[0245] Contact plugs 115 may be formed in the interlayer dielectric layer 110. The interlayer dielectric layer 110 may expose the top surface of the contact plugs 115. The contact plugs 115 may include one or more of the following: semiconductor materials (e.g., polysilicon), metal-semiconductor compounds (e.g., tungsten silicide), conductive metal nitride layers (e.g., titanium nitride, tantalum nitride, or tungsten nitride), and metallic materials (e.g., titanium, tungsten, or tantalum). Although not shown, a plurality of word lines and a plurality of bit lines may be formed on and / or in the substrate 1000. The word lines may intersect the bit lines. The interlayer dielectric layer 110 may be formed to cover the word lines and the bit lines. Impurity regions (not shown) may be formed on the opposite sides of the word lines in the substrate 1000, and the contact plugs 115 may each be connected to one of the impurity regions.

[0246] A mold layer 300 may be formed on the interlayer dielectric layer 110 and the contact plugs 115. The mold layer 300 may include a dielectric semiconductor material, such as a silicon nitride layer.

[0247] The support layer 400 may be formed on the mold layer 300. The support layer 400 may include a material having an etching selectivity with respect to the mold layer 300. The support layer 400 may include, for example, silicon oxide.

[0248] The first mask layer 910 may be formed to cover the support layer 400. The first mask layer 910 may include, for example, one or more of a polysilicon layer, a silicon nitride layer, a silicon oxynitride layer, a spin-on-hardmask (SOH) layer, and an amorphous carbon layer (ACL).

[0249] Reference Figure 4B , an electrode hole 290 may be formed in the support layer 400 and the mold layer 300 to expose the contact plug 115. The formation of the electrode hole 290 may include etching the support layer 400 and the mold layer 300 using the first mask layer 910 as an etching mask. The electrode hole 290 may expose the top surface of the contact plug 115, the inner sidewall of the support layer 400, and the inner sidewall of the mold layer 300.

[0250] Reference Figure 4C , a lower electrode pattern 2000A and a lower electrode column 200 may be formed in the electrode hole 290, thereby forming a lower electrode structure LE. The lower electrode structure LE may include a lower electrode pattern 2000A and a lower electrode column 200. The formation of the lower electrode pattern 2000A and the lower electrode column 200 may include: forming a lower electrode layer on the bottom surface and sidewall of the electrode hole 290 and on the top surface of the support layer 400, forming a preliminary lower electrode column on the lower electrode layer to fill the electrode hole 290, and planarizing (flattening) the lower electrode layer and the preliminary lower electrode column. The planarization process may continue until the support layer 400 is exposed. The lower electrode layer and the preliminary lower electrode column may be planarized to form a lower electrode pattern 2000A and a lower electrode column 200, respectively. The lower electrode pattern 2000A and the lower electrode column 200 may be localized (positioned) in the electrode hole 290.

[0251] The lower electrode layer can be formed by Figure 1 , 2、formed by the thin film forming methods discussed in 3A and 3B. For example, the lower electrode layer may be formed by a deposition process using a deposition precursor including a metal compound according to some exemplary embodiments of the inventive concept. The deposition process may be an atomic layer deposition (ALD) process. In this case, a nitrogen-containing compound may be used as a reaction gas. Accordingly, the lower electrode pattern 2000A may include a niobium-containing nitride layer (e.g., NbNx), a niobium-containing oxide layer (e.g., NbOx), or a niobium-containing oxynitride layer (e.g., NbOxNy) (where x and y are independently positive real numbers). The lower electrode pattern 2000A may not include carbon. The lower electrode pattern 2000A may not include a halogen element. Carbon and halogen elements may act as impurities in the lower electrode pattern 2000A. Accordingly, the lower electrode pattern 2000A may have a low resistivity. The lower electrode structure LE may have a high conductivity. Since the metal compound according to some embodiments has a low melting point and a high vapor pressure, the lower electrode pattern 2000A may be easily manufactured.

[0252] The lower electrode pillar 200 may have a columnar shape. In some embodiments, the lower electrode pillar 200 may have a cylindrical shape. The lower electrode pillar 200 may include one or more of the following: a metallic material (e.g., cobalt, titanium, nickel, tungsten, and / or molybdenum), a metal nitride layer (e.g., a titanium nitride (TiN) layer, a titanium silicon nitride (TiSiN) layer, a titanium aluminum nitride (TiAlN) layer, a tantalum nitride (TaN) layer, a tantalum aluminum nitride layer (TaAlN), and / or a tungsten nitride (WN) layer), a noble metal layer (e.g., platinum (Pt), ruthenium (Ru), and / or iridium (Ir)), a conductive oxide layer (e.g., PtO, RuO 2 、IrO 2 、SRO (SrRuO 3 )、BSRO ((Ba,Sr)RuO 3 )、CRO (CaRuO 3 )、and / or LSCo (La 2-x Sr x CuO 4 , 0 < x < 2)), and / or a metal silicide layer.

[0253] The first mask layer 910 may be removed. The removal of the first mask layer 910 may be performed during and / or after the formation of the lower electrode structure LE.

[0254] Subsequently, refer to Figure 4C and 4D, a second mask layer 920 may be formed on the lower electrode pillar 200 and the support layer 400. The second mask layer 920 may have an opening 929, and the opening 929 may expose a portion of the support layer 400. The second mask layer 920 may include a material having an etching selectivity with respect to the support layer 400.

[0255] The support layer 400 exposed by the second mask layer 920 may be removed to form a support pattern 410 and a preliminary through hole 500P. In some embodiments, the formation of the support pattern 410 may include etching the exposed support layer 400 using the second mask layer 920 as an etching mask. The etching of the support layer 400 may be performed by an anisotropic etching process, and the anisotropic etching process continues until the mold layer 300 is exposed. Therefore, a support pattern 410 and a preliminary through hole 500P may be formed. The preliminary through hole 500P may be spatially connected to the opening 929. The preliminary through hole 500P may expose the top surface of the mold layer 300 and the sidewall of the lower electrode structure LE. For example, the preliminary through hole 500P may expose the top outer sidewall of the lower electrode pattern 2000A.

[0256] Reference Figure 4E , the mold layer 300 may be removed to form the through hole 500 and the empty space 510. The removal of the mold layer 300 may include performing an isotropic etching process on the mold layer 300 exposed to the preliminary through hole 500P. The isotropic etching process may be performed by using, for example, phosphoric acid as an etchant. When etching the mold layer 300, the support pattern 410 may have an etching selectivity and thus may not be removed.

[0257] The lower electrode structure LE may include a plurality of lower electrode structures. As a result of removing the mold layer 300, the preliminary through hole 500P may extend to form a through hole 500. The through hole 500 may be formed between two lower electrode structures LE adjacent to each other. The through hole 500 may expose the top surface of the first portion of the interlayer dielectric layer 110 and the outer sidewalls of the two lower electrode patterns 2000A. The first portion of the interlayer dielectric layer 110 may not overlap with the support pattern 410 vertically. The two lower electrode structures LE may be adjacent to the first portion of the interlayer dielectric layer 110. For example, the lower electrode structure LE may include a first sub-lower electrode structure, a second sub-lower electrode structure, and a third sub-lower electrode structure. The second sub-lower electrode structure may be adjacent to the first sub-lower electrode structure and the third sub-lower electrode structure and between the first sub-lower electrode structure and the third sub-lower electrode structure. The two lower electrode patterns 2000A may be the first sub-lower electrode structure and the second sub-lower electrode structure.

[0258] The empty space 510 may be formed between the interlayer dielectric layer 110 and the supporting pattern 410. The empty space 510 may be formed between the sidewalls of two adjacent lower electrode structures LE. For example, the empty space 510 may be formed between the second sub-lower electrode structure and the third sub-lower electrode structure. The empty space 510 may expose the top surface of the second portion of the interlayer dielectric layer 110, the bottom surface of the supporting pattern 410, and the sidewalls of the two lower electrode structures LE. The second portion of the interlayer dielectric layer 110 may overlap with the supporting pattern 410 in the vertical direction. As used herein in this specification, the term "in the vertical direction" may mean parallel to a direction perpendicular to the top surface of the substrate 1000.

[0259] The second mask layer 920 may be removed to expose the top surface of the support pattern 410. A single etching process may be performed to remove the second mask layer 920 together with the mold layer 300. Alternatively, the second mask layer 920 and the mold layer 300 may be removed by separate processes from each other.

[0260] Reference Figure 4F , a dielectric layer DL may be formed in the through hole 500 and the empty space 510. The dielectric layer DL may conformally cover the top surface of the interlayer dielectric layer 110, the top surface and sidewalls of the lower electrode structure LE, and the top and bottom surfaces of the support pattern 410. The sidewalls of the lower electrode structure LE may correspond to the outer walls of the lower electrode pattern 2000A. The top surface of the lower electrode structure LE may include the top surface of the lower electrode pattern 2000A and the top surface of the lower electrode pillar 200.

[0261] The lower electrode pattern 2000A may serve as a seed (seed) layer for crystallizing the dielectric layer DL. The dielectric layer DL may physically contact the lower electrode pattern 2000A and may have a crystal structure identical to that of the lower electrode pattern 2000A. The dielectric layer DL may have, for example, a tetragonal structure. As a result, the semiconductor device may be improved in electrical characteristics. The dielectric layer DL may be formed using a layer formation technique such as chemical vapor deposition (CVD) or atomic layer deposition (ALD), and / or may have superior step coverage properties.

[0262] The dielectric layer DL may be a single layer or multiple layers. The dielectric layer DL may include a metal oxide, a perovskite structured dielectric, or a combination thereof. The metal oxide may include, for example, one or more of the following: HfO 2 、ZrO 2 、Al 2 O 3 ,La 2 O 3 、 2 O 3 , and TiO 2The perovskite structured dielectric may include one or more of the following: SrTiO 3 (STO), (Ba,Sr)TiO 3 (BST), BaTiO 3 , PZT (lead zirconate titanate), and PLZT (lanthanum-modified lead zirconate titanate).

[0263] Reference Figure 4G , an upper electrode UE may be formed on the dielectric layer DL. The empty space 510 may be filled with an upper electrode UE on the top surface of the dielectric layer DL. The upper electrode UE may be formed by one or more of the following: an impurity-doped semiconductor material, a metallic material, a metal nitride material, and / or a metal silicide material. The metal nitride material may include, for example, one or more of the following: a titanium nitride (TiN) layer, a titanium aluminum nitride (TiAlN) layer, and / or a tungsten nitride (WN) layer. The metallic material may be selected from one of platinum (Pt), ruthenium (Ru), and iridium (Ir). Alternatively, the upper electrode UE may be formed by a refractory metallic material such as cobalt, titanium, nickel, tungsten, and molybdenum. Thus, the semiconductor device 100 may be manufactured.

[0264] According to the present invention, the metal compound of the present invention may have a low melting point and may therefore be easily transported. The metal compound may be used as a deposition precursor. The metal compound according to some embodiments may have a high vapor pressure and may therefore be easily evaporated. When a deposition precursor including the metal compound is used, a deposition process may be easily performed. In some embodiments, the metal compound may not include impurities or may include impurities at an extremely low concentration. Therefore, the deposited thin layer may exhibit excellent characteristics.

[0265] This detailed description of the inventive concept should not be interpreted as being limited to the embodiments set forth herein, and is intended to cover various combinations, modifications and variations of the invention without departing from the spirit and scope of the inventive concept. The appended claims should be interpreted as including other embodiments.

Claims

1. A metal compound comprising a material of Chemical Formula 1: [Chemical formula 1] in: M is Nb or Ta; R is a substituted or unsubstituted C3-C10 alkyl group; and X1, X2, X3, X4 and X5 are each F, Herein, substituted means substituted with at least one substituent selected from the group consisting of a deuterium atom and a halogen atom.

2. The metal compound according to claim 1, wherein R is a substituted or unsubstituted C3-C5 alkyl group.

3. The metal compound according to claim 2, wherein R is a butyl group. The metal compound according to claim 3 , wherein R is sec-butyl. The metal compound according to claim 1 , wherein M is Nb. 6 . The metal compound of claim 1 , wherein the material of Chemical Formula 1 has a melting point in the range of −50° C. to 60° C.

7. The metal compound as claimed in claim 6, wherein the material of Chemical Formula 1 is in a liquid state at 25°C.

8. The metal compound according to claim 1, wherein R is an unsubstituted C3-C10 alkyl group or a halogen-substituted C3-C10 alkyl group.

9. The metal compound according to claim 1, wherein M is Nb and R is butyl.

10. A method for manufacturing a semiconductor device, the method comprising: providing a deposition precursor; and forming a layer with the deposition precursor, The deposition precursor includes a metal compound, and the metal compound includes a material of Chemical Formula 1: [Chemical formula 1] in: M is Nb or Ta; R is a substituted or unsubstituted C3-C10 alkyl group; and X1, X2, X3, X4 and X5 are each independently selected from F, Cl, Br and I, Herein, substituted means substituted with at least one substituent selected from the group consisting of a deuterium atom and a halogen atom.

11. The method of claim 10, wherein X1, X2, X3, X4 and X5 are each independently F or Cl.

12. The method of claim 10, wherein R is a substituted or unsubstituted C3-C5 alkyl group.

13. The method of claim 12, wherein R is butyl.

14. The method of claim 13, wherein R is sec-butyl.

15. The method of claim 10, wherein M is Nb.

16. The method of claim 10, wherein X1, X2, X3, X4 and X5 are each F.

17. The method of claim 10, wherein the material of Chemical Formula 1 has a melting point in the range of -50°C to 60°C.

18. The method of claim 17, wherein the material of Chemical Formula 1 is in a liquid state at 25°C.

19. The method of claim 10, wherein R is an unsubstituted C3-C10 alkyl group or a halogen-substituted C3-C10 alkyl group.

20. The method of claim 10, wherein M is Nb, R is butyl, and X1, X2, X3, X4 and X5 are each F.

21. The method of claim 10, wherein providing a deposition precursor comprises providing the deposition precursor in a precursor storage unit; and the method further comprises transporting the deposition precursor from the precursor storage unit to a precursor supply unit through a supply pipe.

22. The method of claim 10, wherein the layer comprises niobium (Nb) or tantalum (Ta), and the layer is free of carbon.

23. The method of claim 10, further comprising: forming a plurality of lower electrode pillars on the layer to produce a lower electrode structure; forming a dielectric layer on the lower electrode structure; and An upper electrode is formed on the dielectric layer.

24. The method of claim 10, wherein forming a layer with the deposition precursor comprises: supplying the deposition precursor to a chamber including a substrate to form a precursor layer on the substrate; and A reactive gas is contacted with the precursor layer.

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