Aluminum compound and method for manufacturing semiconductor device using the same

Abstract

To provide an aluminum compound as a vapor deposition precursor having thermal stability and transportation availability, and a method for manufacturing a semiconductor device using the same.SOLUTION: An aluminum compound is represented by chemical formula 1 in the figure. R1 and R2 each independently represent a C1-6 alkyl group, a C2-6 dialkylamino group, or the like; Z represents O or N-R7; R3 represents hydrogen, deuterium, or a C1-6 alkyl group; and R4 and R7 each independently represent hydrogen, deuterium, a C1-6 alkyl group, or the like.SELECTED DRAWING: Figure 3B

Description

[Technical Field]

[0001] The present invention relates to an aluminum compound and a method for manufacturing a semiconductor device using the same, and more particularly to an aluminum compound having thermal stability and ease of transportability and a method for manufacturing a semiconductor device using the same. [Background technology]

[0002] 2. Description of the Related Art Due to the development of electronic technology, downscaling of semiconductor devices has progressed at a rapid pace in recent years. Accordingly, the structures of the patterns constituting the semiconductor elements have become more complex and miniaturized.

[0003] Therefore, when forming thin films containing aluminum, it is necessary to develop a raw material compound that can ensure thermal stability and form thin films with a complex and fine three-dimensional structure and uniform thickness. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] U.S. Patent No. 9,255,324 [Patent Document 2] U.S. Patent No. 9,663,538 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above-mentioned problems in conventional semiconductor devices, and an object of the present invention is to provide an aluminum compound as a vapor deposition precursor having thermal stability and ease of transport. Another object of the present invention is to provide a method for manufacturing a semiconductor device, which includes forming a thin film having a small thickness and improved properties using the deposition precursor. [Means for solving the problem]

[0006] The aluminum compound according to the present invention, which has been made to achieve the above object, is characterized by being represented by the following chemical formula 1. [ka] In the above formula 1, R 1 and R 2 are each independently one selected from an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having 2 to 6 carbon atoms, an alkoxide group having 1 to 6 carbon atoms, and a halogen element, and Z is O or NR 7 and R 3 is any one selected from hydrogen, deuterium, and an alkyl group having 1 to 6 carbon atoms; R 4 and R 7 are each independently one selected from hydrogen, deuterium, an alkyl group having 1 to 6 carbon atoms, and a dialkylamino alkyl group having 3 to 10 carbon atoms; R 5 and R 6 are each independently one selected from hydrogen, deuterium, and an alkyl group having 1 to 6 carbon atoms.

[0007] To achieve the above object, a method for manufacturing a semiconductor device according to the present invention includes the steps of preparing a deposition precursor containing an aluminum compound and forming a thin film using the deposition precursor, wherein the aluminum compound is represented by Chemical Formula 1 below. [ka] In the above formula 1, R 1 and R 2 are each independently one selected from an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having 2 to 6 carbon atoms, an alkoxide group having 1 to 6 carbon atoms, and a halogen element, and Z is O or NR 7 and R 3is any one selected from hydrogen, deuterium, and an alkyl group having 1 to 6 carbon atoms; R 4 and R 7 are each independently one selected from hydrogen, deuterium, an alkyl group having 1 to 6 carbon atoms, and a dialkylamino alkyl group having 3 to 10 carbon atoms; R 5 and R 6 are each independently one selected from hydrogen, deuterium, and an alkyl group having 1 to 6 carbon atoms. [Effects of the Invention]

[0008] According to the aluminum compound and the method for manufacturing a semiconductor device using the same according to the present invention, the aluminum compound has a low melting point and can be easily transported. Aluminum compounds can be used as vapor deposition precursors and have excellent stability. The deposition process can have a wide deposition window, and a thin film can be formed to a small thickness by a deposition process including a deposition precursor, and the thin film exhibits improved properties. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a flowchart illustrating a vapor deposition process using an aluminum compound according to an embodiment of the present invention. [Figure 2] 1 is a diagram illustrating a schematic diagram of a vapor deposition system according to an embodiment of the present invention. [Figure 3A] 1 is a schematic cross-sectional view illustrating the formation of a thin film according to an embodiment of the present invention. [Figure 3B] 1 is a schematic cross-sectional view illustrating the formation of a thin film according to an embodiment of the present invention. [Figure 4A] 1A to 1C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to an embodiment of the present invention. [Figure 4B] 1A to 1C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to an embodiment of the present invention. [Figure 4C]1A to 1C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to an embodiment of the present invention. [Figure 4D] 1A to 1C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to an embodiment of the present invention. [Figure 4E] 1A to 1C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to an embodiment of the present invention. [Figure 4F] 1A to 1C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to an embodiment of the present invention. [Figure 4G] 1A to 1C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to an embodiment of the present invention. [Figure 4H] 1A to 1C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to an embodiment of the present invention. [Figure 4I] 1A to 1C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to an embodiment of the present invention. [Figure 4J] 1A to 1C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to an embodiment of the present invention. [Figure 5A] 5A to 5C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to another embodiment of the present invention. [Figure 5B] 5A to 5C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to another embodiment of the present invention. [Figure 5C] 5A to 5C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to another embodiment of the present invention. [Figure 5D] 5A to 5C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to another embodiment of the present invention. [Figure 5E] 5A to 5C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to another embodiment of the present invention. [Figure 5F] 5A to 5C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to another embodiment of the present invention. [Figure 5G] 5A to 5C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to another embodiment of the present invention. [Figure 5H]5A to 5C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to another embodiment of the present invention. [Figure 5I] 5A to 5C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to another embodiment of the present invention. [Figure 6A] 10A to 10C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to still another embodiment of the present invention. [Figure 6B] 10A to 10C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to still another embodiment of the present invention. [Figure 6C] 10A to 10C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to still another embodiment of the present invention. [Figure 6D] 10A to 10C are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to still another embodiment of the present invention. [Figure 7A] 1 is a plan view showing a partial schematic configuration of a semiconductor element according to an embodiment of the present invention. [Figure 7B] FIG. 7B is a schematic perspective view of the semiconductor device of FIG. 7A. [Figure 7C] 7B is a schematic cross-sectional view illustrating a method for manufacturing a semiconductor device according to an embodiment of the present invention, taken along lines II' and II-II' in FIG. 7A. [Figure 8] 1 is a graph showing the results of the film thickness deposited per cycle as a function of temperature. DETAILED DESCRIPTION OF THE INVENTION

[0010] Next, specific examples of embodiments for carrying out the aluminum compound according to the present invention and the method for manufacturing a semiconductor device using the same will be described with reference to the drawings.

[0011] As used herein, "substituted or unsubstituted" may mean substituted or unsubstituted with one or more substituents selected from the group consisting of hydrogen atoms, deuterium atoms, halogen atoms, cycloalkyl, aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, aryloxy, alkylthio, arylthio, cyano, halogen, carbonyl, amino, and derivatives thereof. Additionally, each of the exemplified substituents may be substituted or unsubstituted. For example, a methylamino group can be interpreted as an amino group. As used herein, an alkyl group is a straight chain alkyl group, a branched alkyl group, or a cyclic alkyl group. The number of carbon atoms in the alkyl group is not particularly limited, but it is an alkyl group having 1 to 6 carbon atoms. In this specification, the number of carbon atoms in the amine / amino group is not particularly limited, but is 1 or more and 6 or less. The amine may include at least one of an aliphatic amine having 1 to 6 carbon atoms and a cyclic amine having 3 to 6 carbon atoms. The amino group can include an alkylamino group. The alkylamino group can include a monoalkylamino group and a dialkylamino group. As used herein, halogen elements may include fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0012] Unless otherwise defined in the chemical formulas herein, if a chemical bond is not drawn at a position where a chemical bond is required, this may mean that a hydrogen atom is bonded to that position. In this specification, normal temperature means 25°C. In this specification, like reference numbers refer to like elements throughout. Hereinafter, an aluminum compound and a method for producing the same according to an embodiment of the present invention will be described.

[0013] The aluminum compound according to an embodiment of the present invention is represented by the following Chemical Formula 1. [ka] In formula 1, R 1 and R 2 are each independently any one selected from an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having 2 to 6 carbon atoms, an alkoxide group having 1 to 6 carbon atoms, and a halogen element. Z is O or NR 7 and R 3 is any one selected from hydrogen, deuterium, and an alkyl group having 1 to 6 carbon atoms, R 4 and R 7 are each independently one selected from hydrogen, deuterium, alkyl having 1 to 6 carbon atoms, and dialkylaminoalkyl having 3 to 10 carbon atoms; R 5 and R 6 are each independently one selected from hydrogen, deuterium, and an alkyl group having 1 to 6 carbon atoms.

[0014] In formula 1, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 When is an alkyl group, the alkyl group has 1 to 6 carbon atoms, more specifically 1 to 4 carbon atoms. The number of carbon atoms in a dialkylaminoalkyl ((Dialkylamino)Alkyl) group means the total number of carbon atoms in the dialkylaminoalkyl group. In formula 1, Z is NR 7 When N is bonded to Al, In Chemical Formula 1, examples of the alkyl group having 1 to 6 carbon atoms include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, amyl, and / or isoamyl, and hexyl.

[0015] Dialkylamino having 2 to 6 carbon atoms can include Dimethylamino, Diethylamino, Dipropylamino, Diisopropylamino, EthylMethylamino, PropylMethylamino, and / or IsopropylMethylamino. Alkoxides having 1 to 6 carbon atoms can include, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentoxy, isopentoxy, and / or tert-pentoxy. The halogen elements can include F, Cl, and / or Br. Dialkylaminoalkyl having 3 to 10 carbon atoms can include, for example, DimethylaminoMethyl, EthylMethylaminoMethyl, DiethylaminoMethyl, DimethylaminoEthyl, EthylMethylaminoEthyl, and / or DiethylaminoEthyl.

[0016] The aluminum compound represented by Chemical Formula 1 is any one selected from Compound Group A (No. 1 to No. 85) shown below. [ka] [ka] [ka] [ka] [ka] [ka]

[0017] In No. 1 to No. 85 of compound group A, Me is a methyl group, Et is an ethyl group, iPr is an isopropyl group, sBu is a sec-butyl group, tBu is a tert-butyl group, and DMA is a dimethylamino group.

[0018] iPr can be represented by the following chemical formula 2A. [ka] sBu can be represented by the following chemical formula 2B. [ka]

[0019] tBu can be represented by the following chemical formula 2C. [ka] DMA can be represented by the chemical formula 2D shown below. [ka] In Chemical Formulae 2A to 2D, * represents the corresponding bonded moiety among C, N, and O of Compounds No. 1 to No. 85 of Compound Group A.

[0020] Aluminum compounds can be used as vapor deposition precursors. For example, aluminum compounds can be used as vapor deposition precursors in atomic layer deposition or chemical vapor deposition (CVD). The greater the stability (eg, thermal stability) of the deposition precursor, the better the properties of the deposited film.

[0021] According to an embodiment of the present invention, the aluminum compound has an aluminum-nitrogen (Al-N) bond or an aluminum-oxygen (Al-O) bond (Al-Z bond in Chemical Formula 1). When aluminum is directly bonded to nitrogen or oxygen, the bonding strength between aluminum and the other element bonded to aluminum increases. That is, aluminum-nitrogen (Al-N) bonds or aluminum-oxygen (Al-O) bonds are provided, so that aluminum and R 1 The bonding strength between aluminum and R 2 The bonding strength between them increases. Therefore, the aluminum compound can have excellent stability.

[0022] The aluminum compound contains nitrogen at the 5-position as shown in Chemical Formula 3 below, and the nitrogen may have an unshared electron pair. The nitrogen's lone electron pair interacts with the aluminum as shown by the dotted line. The interaction between aluminum and nitrogen at the 5-position is an intramolecular interaction. The above interaction causes the aluminum compound to form a hexagonal ring structure. Compounds with hexagonal ring structures are stable. Therefore, the stability of the aluminum compound is further increased. [ka] In formula 3, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and Z are the same as defined in Chemical Formula 1.

[0023] The aluminum compound has a conjugation system and forms a resonance structure. Therefore, the stability of the aluminum compound is improved. The stability of the aluminum compound includes thermal stability. For example, aluminum compounds have relatively high thermal decomposition temperatures. Aluminum compounds have a thermal decomposition temperature of about 300°C to 600°C. When aluminum compounds are used as deposition precursors, the properties of the deposited thin films can be improved. The thin film has a high density. If the aluminum compound has a thermal decomposition temperature lower than 300° C., the properties of the deposited thin film may be deteriorated or restrictions may be imposed on the deposition process conditions.

[0024] When an aluminum compound is used as a deposition precursor, the deposition process can have a relatively wide deposition window. The deposition window can refer to the temperature range in which the deposition process can be carried out when using certain deposition precursors. The deposition window may include an atomic layer deposition window (ALD window). The deposition process can be carried out at a temperature even lower than the thermal decomposition temperature of the deposition precursor. According to an embodiment, the aluminum compound has a high thermal decomposition temperature. When an aluminum compound is used as the vapor deposition precursor, the vapor deposition process can be carried out at a higher temperature. Therefore, the constraints on deposition process conditions are reduced.

[0025] According to an embodiment of the present invention, the aluminum compound has a low melting point. The aluminum compound has a melting point of, for example, -50°C to 45°C. The aluminum compound is in a liquid state at room temperature (for example, 25°C). Alternatively, less energy is required to provide the aluminum compound in a liquid state. Therefore, the aluminum compound can be easily transported in a liquid state.

[0026] The aluminum compound may contain no impurities or may contain low levels of impurities. Impurities refer to substances other than the substance represented by Chemical Formula 1. The impurities may include metal-containing impurities, halogen-containing impurities, and / or organic impurities. The concentration of metal impurities is less than 1 ppm. Specifically, the concentration of metal impurities is 0 to 1 ppm. In this specification, the concentration of some impurities being "0" can mean that the impurity is not contained. More specifically, the concentration of metal impurities is 100 ppb or less. When the metal impurities contain a plurality of different metal elements, the concentration of each metal element is 100 ppb or less, more specifically 1 ppb or less. The metal impurities may include alkali metals and / or alkaline earth metals. If the insulating film contains the above metal elements, the properties of the insulating film may be deteriorated.

[0027] Halogen-containing impurities may include fluorine, chlorine, and / or bromine. The concentration of halogen-containing impurities is less than or equal to 100 ppm. Specifically, the concentration of halogen-containing impurities is 10 ppm, more specifically 1 ppm or less. The concentration of organic impurities is below 500 ppm. The concentration of organic impurities is less than 50 ppm, more particularly less than 10 ppm. The aluminum compound may contain no water or a low concentration of water. The concentration of water in the aluminum compound is 10 ppm or less, particularly 1 ppm or less.

[0028] When the aluminum compound is in a liquid state, the impurities may be present in particulate form. The content of impurity particles is low. The impurity particles may have a small diameter. When the diameter of the impurity particles is larger than 0.3 μm, the number of the impurity particles is 100 or less in 1 mL of the aluminum compound. When the diameter of the impurity particles is larger than 0.2 μm, the number of the impurity particles is 100 or less in 1 mL of the aluminum compound.

[0029] If the deposition precursor contains impurities, contaminant particles can form in or on the deposited thin film. According to embodiments of the present invention, the aluminum compound may contain no impurities or may contain very low concentrations of impurities. Therefore, the deposited thin film exhibits excellent properties. Aluminum compounds according to embodiments of the present invention can have high vapor pressures and can be easily vaporized. When a vapor deposition precursor containing an aluminum compound is used, the vapor deposition process can be easily carried out. The aluminum compound can be prepared using a diketimine compound or a ketoimine compound as a reactant. Specific examples of producing the aluminum compound will be explained in Examples 1 to 12 below. The deposition process and thin film formation method using an aluminum compound will now be described.

[0030] FIG. 1 is a flowchart illustrating a vapor deposition process using an aluminum compound according to an embodiment of the present invention, FIG. 2 is a schematic diagram illustrating a vapor deposition system according to an embodiment of the present invention, and FIGS. 3A and 3B are schematic cross-sectional views illustrating the formation of a thin film according to an embodiment of the present invention.

[0031] Referring to FIG. 1, the deposition process includes a step of preparing a deposition precursor containing an aluminum compound (step S10), a step of supplying the deposition precursor to form a precursor layer (step S20), and a step of supplying a reaction gas to form a thin film (step S30). The deposition process may further include a step of performing a first evacuation process (step S21) and a step of performing a second evacuation process (step S31). The deposition process is an atomic layer deposition process.

[0032] 1 to 3, a deposition system 1 includes a chamber 10, a precursor supply unit 20, and a reactive gas supply unit 30. The deposition system 1 can be used for atomic layer deposition processes. Alternatively, the deposition system 1 can be used for chemical vapor deposition processes. A substrate 1000 is loaded into the chamber 10 . Substrate 1000 is a wafer substrate such as a semiconductor wafer.

[0033] A vapor deposition precursor 2001 containing an aluminum compound is prepared (step S10). The deposition precursor 2001 is transported and provided in the precursor supply unit 20 . Aluminum compounds have low melting points, allowing the deposition precursor 2001 to be easily transported in a liquid state. For example, an aluminum compound is provided in a liquid state in the precursor containment vessel. The precursor supply unit 20 may be configured to have a precursor storage vessel disposed therein.

[0034] As another example, an aluminum compound can be dissolved in an organic solvent to prepare a precursor solution. When the vapor deposition precursor is provided in the form of a precursor solution, the concentration of the vapor deposition precursor relative to the organic solvent is 0.01 mol / L to 2.0 mol / L, particularly 0.05 mol / L to 1.0 mol / L. A precursor solution is provided in a precursor containment vessel. Thereafter, a precursor containment vessel is provided in the precursor supply unit 20 . The precursor supply unit 20 supplies the deposition precursor to the interior space of the chamber 10 .

[0035] The organic solvent may include an acetic ester solvent, an ether solvent, a ketone solvent, a hydrocarbon solvent, and / or a heteroaromatic ring solvent. The concentration of water in the organic solvent is 10 ppm or less, specifically 1 ppm or less. The acetate solvent may include ethyl acetate, butyl acetate, and / or methoxyethyl acetate. The ether solvent can include tetrahydrofuran, tetrahydropyrane, ethylene glycol dimethylether, diethylene glycol dimethylether, triethylene glycol dimethylether, dibutylether, and / or dioxane. The ketone solvent can include methylbutylketone, methylisobutylketone, ethylbutylketone, dipropylketone, diisobutylketone, methylamylketone, cyclohexanone, and / or methylcyclohexanone.

[0036] The hydrocarbon solvent can include unsaturated hydrocarbon solvents and saturated hydrocarbon solvents. The hydrocarbon solvent can include hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, toluene, and / or xylene. The hydrocarbon solvent is a hydrocarbon solvent having a cyano group. In this case, the hydrocarbon solvent having a cyano group can include 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane, and / or 1,4-dicyanobenzene. The heteroaromatic ring solvent may include pyridine and / or lutidine.

[0037] Vapor deposition precursor 2001 may further include additional precursors in addition to the aluminum compound. The additional precursors may be provided into the chamber 10 through a supply passage separate from the aluminum compound. As another example, an aluminum compound and an additional precursor may be mixed to produce a mixed precursor. A mixture of precursors may be provided into the chamber 10 . The additional precursors include, but are not limited to, at least one of a semiconductor compound, a metal compound, and an organic compound. The concentration of water in the additional precursor is 10 ppm or less, particularly 1 ppm or less.

[0038] The semiconductor compound may include silicon and / or germanium. Metal compounds include magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, manganese, iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, argentum, aurum, zinc, gall. ium, indium, germanium, tin, lead, antimony, bismuth, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, and / or ytterbium.

[0039] The organic compound may include at least one of an alcohol compound, a glycol compound, a beta-diketone compound, a cyclopentadiene compound, and an amine compound. The organic compound provides the organic ligand, and the deposited thin film may include the organic ligand.

[0040] The alcohol compound can include, for example, an alkyl alcohol compound or an ether alcohol compound. The alkyl alcohol compound means an alcohol compound having an alkyl group. For example, the alkyl alcohol compound can include methanol, ethanol, propanol, isopropyl alcohol, butanol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, pentyl alcohol, isopentyl alcohol, and / or tert-pentyl alcohol.

[0041] The ether alcohol compound means an alcohol compound having an ether group. For example, the ether alcohol compound can include 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-s-Butoxy-1,1-Diethylethanol, and / or 3-Methoxy-1,1-Dimethylpropanol.

[0042] The glycol compound can include, for example, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 2,4-hexanediol, 2,2-Dimethyl-1,3-propanediol, 2,2-Diethyl-1,3-propanediol, 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 / or 2,4-Dimethyl-2,4-Pentanediol.

[0043] The beta-diketone compound can include alkyl-substituted beta-diketone compounds, fluorine-substituted beta-diketone compounds, and / or ester-substituted beta-diketone compounds. Alkyl-substituted beta-diketone compounds include 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, and 2,2,6-trimethicone. The methyloctane-2,4-dione may include 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 / or 2,2-dimethyl-6-ethyldecane-3,5-dione.

[0044] Fluorine-substituted beta-diketone compounds can include 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 / or 1,3-DiperfluoroHexylpropane-1,3-dione. The ester-substituted beta-diketone compounds can include 1,1,5,5-tetraMethyl-1-Methoxyhexane-2,4-dione, 2,2,6,6-tetraMethyl-1-Methoxyheptane-3,5-dione, and / or 2,2,6,6-tetraMethyl-1-(2-MethoxyEthoxy)heptane-3,5-dione.

[0045] Cyclopentadiene compounds can include Cyclopentadiene, MethylCyclopentadiene, EthylCyclopentadiene, PropylCyclopentadiene, IsopropylCyclopentadiene, ButylCyclopentadiene, Sec-ButylCyclopentadiene, IsobutylCyclopentadiene, Tert-ButylCyclopentadiene, DimethylCyclopentadiene, and / or tetraMethylCyclopentadiene.

[0046] The amine compound can include Methylamine, Ethylamine, Propylamine, Isopropylamine, Butylamine, Sec-Butylamine, Tert-Butylamine, Isobutylamine, Dimethylamine, Diethylamine, Dipropylamine, Diisopropylamine, EthylMethylamine, PropylMethylamine, and / or IsopropylMethylamine.

[0047] As shown in FIGS. 1, 2, and 3A, a deposition precursor 2001 is supplied into the chamber 10 to form a precursor layer 2100 on the substrate 1000 (step S20). The vapor deposition precursor 2001 includes the aluminum compounds previously described. A vapor deposition precursor 2001 is adsorbed onto the top surface 1000 A of the substrate 1000 to form a precursor layer 2100 . While the deposition precursor 2001 is being supplied into the chamber 10, the temperature of the substrate 1000 may be maintained at 25°C to 400°C, specifically 200°C to 300°C. By supplying the vapor deposition precursor 2001 into the chamber 10, the pressure in the chamber 10 is 10 Pa to 1,013 hPa.

[0048] The deposition precursor 2001 can be delivered into the chamber 10 by pneumatic transport. The vapor deposition precursor 2001 in a liquid state is heated and depressurized in the precursor supply unit 20, and the vapor deposition precursor 2001 is vaporized. As another example, the deposition precursor 2001 can be delivered into the chamber 10 by a liquid transport method. In this case, a separate vaporization chamber (not shown) may be provided between the precursor supply unit 20 and the chamber 10 . The deposition precursor 2001 is delivered to the vaporization chamber in a liquid state. The deposition precursor 2001 is vaporized by heating and reducing pressure in the vaporization chamber. Thus, vapor deposition precursor 2001 in gaseous state is formed. The vapor deposition precursor 2001 in a gaseous state is supplied into the chamber 10 either alone or together with a carrier gas. The carrier gas includes an inert gas such as argon, nitrogen, and / or helium.

[0049] After the precursor layer 2100 is formed, a first evacuation step is performed (step S21). During the first evacuation step, remaining deposition precursor 2001 and by-product gases are removed from the chamber 10 . The first evacuation step can include a purging step, a depressurization step, or a combination thereof. For example, the purging step is performed by supplying an inert gas into the chamber 10 . Inert gases include argon, nitrogen, and / or helium. The depressurization step involves reducing the pressure within the chamber 10 . The decompression step is carried out until the pressure inside the chamber 10 reaches 0.01 Pa to 300 Pa, specifically, 0.01 Pa to 100 Pa.

[0050] As shown in FIGS. 1, 2, and 3B, a reaction gas is supplied into the chamber 10 to form a thin film (step S30). The reactive gas reacts with the precursor layer 2100 . For example, the reactive gas reacts with the deposition precursor 2001 adsorbed on the substrate 1000 . Thus, a thin film 2000 is formed on the substrate 1000 . The reactive gas may include at least one of an oxidizing gas, a reducing gas, and / or a nitrogen-containing gas.

[0051] The oxidizing gas may include, for example, oxygen, ozone, nitrogen dioxide, nitric oxide, water vapor, hydrogen peroxide, acetic acid, and / or acetic anyhydride. The reducing gas may include hydrogen. The nitrogen-containing gas may include an organic amine compound, a hydrazine compound, and / or ammonia. The organic amine compound can include a mono(alkyl)amine, a dialkylamine, a trialkylamine, and / or an alkylenediamine. As another example, the reactive gas may include NO2, N2O (nitrous oxide), CO2, H2O2, HCOOH, CH3COOH, and / or (CH3CO)2O.

[0052] When a nitrogen-containing gas is used as the reactant gas, the deposited thin film 2000 comprises an aluminum nitride film or an aluminum-containing composite nitride film. When an oxidizing gas is used as the reactant gas, the deposited thin film 2000 contains oxygen. For example, the deposited thin film 2000 comprises an aluminum oxide film or an aluminum-containing composite oxide film. While the reaction gas is being supplied into the chamber 10, the temperature of the substrate 1000 is maintained at 25°C to 400°C, specifically 200°C to 300°C. While the reaction gas is being supplied into the chamber 10, the pressure inside the chamber 10 is 10 Pa to 1,013 hPa.

[0053] According to an embodiment of the present invention, the deposition process temperature is 300 to 600°C. The deposition process temperature refers to the temperature inside the chamber 10 . The deposition process temperature may include at least one of the temperature of the chamber 10 in the step of supplying the deposition precursor (step S20) and the temperature of the chamber 10 in the step of supplying the reaction gas (step S30). The pressure in the chamber 10 in the step of supplying the reaction gas (step S30) is 10 Pa to 1,013 hPa.

[0054] Energy can be added to the chamber 10 during the deposition process. The energy can include at least one of plasma, light, heat, and voltage. For example, the deposition process is carried out by atomic layer vapor deposition. The step of adding energy can be performed in at least one of the steps of supplying a precursor gas (step S20), performing a first exhaust step (step S21), supplying a reaction gas (step S30), or performing a second exhaust step (step S31). The deposition process can be carried out by thermal chemical vapor deposition (therma CVD), plasma chemical vapor deposition (plasma CVD), photo chemical vapor deposition (photo CVD), or photoplasma chemical vapor deposition (photoplasma CVD).

[0055] According to an embodiment of the present invention, the material of the thin film 2000 can be determined by the aluminum compound, the type of reactive gas, and the type of additional deposition precursor 2001 in the deposition process. The thin film 2000 may include an aluminum-containing film. The aluminum-containing film can include metals, oxide ceramics, and / or nitride ceramics. The aluminum-containing film can include, for example, an aluminum film, an aluminum nitride film, an aluminum oxide film, and / or an aluminum composite oxide film. The aluminum composite oxide film can include an aluminum oxynitride film, an aluminum metal oxide film, and / or an aluminum oxycarbide film. The aluminum metal oxide film can contain aluminum and a metal other than aluminum.

[0056] As another example, the aluminum composite oxide film may include AlSixOy, ZrAlxSiOy, TiAlxSixOy, and / or HfAlxSiOy (x and y are each real numbers). For example, the aluminum composite oxide film is AlSi 0.8~1.2 O 3.1~3.9 , ZrAl2SiO7, TiAl2SiO7, and / or HfAl2SiO7 (x and y are each real numbers).

[0057] The deposition rate of the thin film 2000 can be adjusted by the supply conditions of the deposition precursor 2001 , the temperature of the substrate 1000 , and the pressure in the chamber 10 . The supply conditions of the vapor deposition precursor 2001 include the vaporization temperature of the vapor deposition precursor 2001 and the pressure of the vaporized vapor deposition precursor 2001 . The deposition rate can determine the thickness of the thin film 2000 deposited per cycle. When the deposition process is carried out by atomic layer deposition, the deposition rate can be evaluated by the thickness of the thin film 2000 deposited per cycle. Unless otherwise stated in the following description, the thickness of the thin film 2000 refers to the thickness of the thin film 2000 deposited per cycle. The cycle refers to a process for forming a single layer of thin film 2000. For example, the step of supplying the deposition precursor 2001 (step S20), the first exhaust process step (step S21), the step of supplying the reaction gas (step S30), and the second exhaust process step (step S31) in FIG. 1 constitute one cycle.

[0058] If the deposition rate is too slow (eg, less than 0.01 nm / min), the productivity of the thin film 2000 may decrease. If the deposition rate is too fast (eg, above 100 nm / min), the thin film 2000 may be deposited to a large thickness, which may reduce the properties of the thin film 2000. According to an embodiment of the present invention, the aluminum compound has thermal stability and a deposition rate of 0.05 nm / min to 100 nm / min, particularly 1 nm / min to 50 nm / min. Thus, the thin film 2000 can have a small thickness and exhibit improved properties.

[0059] For example, the deposition thickness of 2000 thin films per cycle is 0.05 Å to 0.6 Å. According to embodiments of the present invention, the thickness of the thin film 2000 is reduced, allowing for smaller semiconductor devices and finer pitches. Therefore, when using the aluminum compound represented by Chemical Formula 1, the thin film 2000 can be deposited to a smaller thickness. After the formation of the thin film 2000, an annealing step may further be performed on the thin film 2000. The annealing step can be carried out in an inert gas atmosphere, an oxidizing gas atmosphere, or a reducing gas atmosphere. The annealing process may improve the electrical properties of the thin film 2000 . In this case, the electrical properties may include insulating properties. The annealing process allows the thin film 2000 to become dense.

[0060] After the formation of the thin film 2000, a reflow process can further be performed on the thin film 2000. The reflow process can improve the step coverage of the thin film 2000 . The reflow process can be carried out at a temperature of 250°C to 1000°C, specifically 300°C to 500°C. After the thin film 2000 is formed, a second evacuation step is carried out (step S31). During the second evacuation process in step (S31), reacted and remaining reactant gases and by-product gases are removed from the chamber 10. The second evacuation step may include a purging step, a depressurization step, or a combination thereof, as described for the first evacuation step.

[0061] According to an embodiment of the present invention, after the step of supplying the deposition precursor 2001 (step S20), the step of supplying the reaction gas (step S30) is performed. As another example, the step of supplying the reaction gas (step S30) can be performed simultaneously with the step of supplying the deposition precursor 2001 (step S20). In this case, the first exhaust process step (step S21) may be omitted.

[0062] The above-described process of forming the thin film 2000 can be performed multiple times on the substrate 1000. For example, the thin film 2000 formation process cycle is repeated. In this case, the thin film 2000 may include multiple thin films 2000 stacked together. Thus, the total thickness of the thin film 2000 can be adjusted. According to an embodiment of the present invention, the thin film 2000 may be used as, but is not limited to, wiring in an integrated circuit, a hard coating film in a component, a gate insulating film in a transistor, an insulating film in a memory element, a dielectric film in a hard capacitor, a magnetoresistive head in a hard disk, an optical glass in an optical communication circuit, and / or a catalyst.

[0063] 4A to 4J are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to an embodiment of the present invention. Referring to FIG. 4A, a substrate 1000A including a plurality of active regions AC is provided. The substrate 1000A is a semiconductor substrate. The active area AC is defined by the element isolation area 112 . The element isolation regions 112 are interposed between the active regions AC. The isolation region 112 may include a silicon-based insulating material. The silicon-based insulating material may include silicon oxide, silicon nitride, silicon oxynitride, or a combination thereof.

[0064] An interlayer insulating film 120 is formed on the substrate 1000A. The interlayer insulating film 120 may include a silicon oxide film. A conductive portion 124 is formed in the interlayer insulating film 120 and connected to the active region AC. The conductive portion 124 penetrates the interlayer insulating film 120 . The plurality of conductive portions 124 may include polysilicon, metal, conductive metal nitride, metal silicide, or a combination thereof.

[0065] Referring to FIG. 4B, an insulating layer 128 is formed on the interlayer insulating film 120 and the conductive portion 124. The insulating layer 128 acts as an etch stop layer. The insulating layer 128 is made of an insulating material having an etching selectivity with respect to the interlayer insulating film 120 and a mold film (130 in FIG. 4C) to be formed in a subsequent process. The insulating layer 128 may include, for example, a silicon-based insulating material.

[0066] Referring to FIG. 4C, a molding film 130 is formed on the insulating layer 128. The mold film 130 may include an oxide film.

[0067] Referring to FIG. 4D, a sacrificial pattern 142 and a mask pattern 144 are sequentially formed on the mold film 130. The sacrificial pattern 142 may include an oxide layer. The sacrificial pattern 142 serves to protect the upper part of the mold film 130 . The mask pattern 144 may include an oxide film, a nitride film, a polysilicon film, a photoresist film, or a combination thereof.

[0068] Referring to FIG. 4E, the sacrificial pattern 142 and the mold film 130 are etched using the mask pattern 144 as an etching mask. The etching is a dry etching. A plurality of holes H1 are formed in the sacrificial pattern 142 and the mold layer 130 by an etching process. The holes H1 are spaced apart from each other and penetrate the sacrificial pattern 142 and the mold film 130. At this time, the insulating layer 128 is further etched so that the hole H1 extends into the insulating layer 128. The hole H1 exposes the conductive portion 124. Thereafter, the mask pattern 144 is removed to expose the top surface of the sacrificial pattern 142 .

[0069] Referring to FIG. 4F, a conductive film 150 is formed in the hole H1 and on the sacrificial pattern 142. The conductive film 150 conformally covers the upper surface of the conductive portion 124 exposed by the hole H1, the inner wall of the insulating layer 128, the inner wall of the mold film 130, and the inner wall and upper surface of the sacrificial pattern 142. The conductive film 150 can be, for example, a doped semiconductor, a conductive metal nitride, a metal, a metal silicide, a conductive oxide, or a combination thereof. The conductive film 150 can be made of, for example, 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 conductive film 150 can be formed by a deposition process. For example, the conductive film 150 can be formed by chemical vapor deposition (CVD), metal organic chemical vapor deposition (MOCVD), or atomic layer deposition (ALD).

[0070] Referring to FIG. 4G, the upper portion of the conductive film 150 is removed to form a plurality of lower electrodes LE. Removal of the conductive film 150 can be performed by an etch-back process or a chemical mechanical polishing (CMP) process. In the process of removing the conductive film 150, the sacrificial pattern 142 is also removed. The conductive film 150 is removed until the upper surface of the mold film 130 is exposed. Each of the lower electrodes LE has a cylindrical shape. Unlike the one shown in the figure, the lower electrode LE may be a pillar-shaped lower electrode without an internal space.

[0071] Referring to FIG. 4H, the mold film 130 is removed to expose the outer wall of the lower electrode LE and the upper surface of the insulating layer 128. The mold film 130 is removed by an etching process. The etching step may include a dry etching step.

[0072] Referring to FIG. 4I, a dielectric film 2000A is formed to cover the bottom electrode LE. The dielectric film 2000A may conformally cover the exposed surfaces of the bottom electrode LE, where the exposed surfaces include the inner and outer surfaces and the top surface of the bottom electrode LE. Dielectric film 2000A further covers the top surface of insulating layer 128. The dielectric film 2000A can be formed by the thin film formation method previously described with reference to FIGS. 1, 2, 3A, and 3B. For example, the dielectric film 2000A is formed by a vapor deposition process using a vapor deposition precursor containing an aluminum compound of the present invention. The deposition process is an atomic layer deposition (ALD) process. The aluminum compound according to the embodiment of the present invention has thermal stability and can form the dielectric film 2000A to a small thickness. For example, the dielectric film 2000A is a single thin film having a thickness of 0.05 Å to 0.6 Å. As another example, the dielectric film 2000A includes a plurality of thin films, each having a thickness of 0.05 Å to 0.6 Å.

[0073] The dielectric film 2000A exhibits excellent properties, including insulating properties. The dielectric film 2000A may include an aluminum-containing film. As an example, the dielectric film 2000A may include an aluminum oxide film and a high-k film. In this case, the aluminum oxide film can be formed by the thin film formation method described with reference to FIGS. 1, 2, 3A, and 3B. The high dielectric film may include hafnium oxide, tantalum oxide, and / or zirconium oxide. The high dielectric film may have a crystalline structure. As the thickness of the aluminum oxide film decreases, the high dielectric film can have an improved crystalline structure. Therefore, the dielectric constant of the dielectric film 2000A is improved.

[0074] The bottom electrode LE has a relatively large aspect ratio to improve the capacitance of the capacitor (170 in FIG. 4J). The deposition process using an aluminum compound according to an embodiment of the present invention as a deposition precursor exhibits excellent step coverage properties. Therefore, the dielectric film 2000A can seal the lower electrode LE well. The deposition process is carried out at a temperature of 300°C to 600°C. The formation of the dielectric film 2000A may further include a step of annealing at 500°C to 1150°C.

[0075] Referring to FIG. 4J, an upper electrode UE is formed on the dielectric film 2000A. The upper electrode UE may comprise a conductive material such as a doped semiconductor, a conductive metal nitride, a metal, a metal silicide, and / or a conductive oxide. The top electrode UE can be formed by chemical vapor deposition (CVD), metal organic chemical vapor deposition (MOCVD), or atomic layer deposition (ALD). The lower electrode LE, the dielectric film 2000A, and the upper electrode UE form a capacitor 170. The manufacturing of the semiconductor device 100 is completed by the manufacturing example described above. The semiconductor device 100 includes a capacitor 170 . The manufacturing process of the semiconductor device 100 includes the step of depositing a dielectric film 2000A.

[0076] 5A to 5I are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to another embodiment of the present invention. Referring to FIG. 5A, an etch stop film 222, a sacrificial layer 224, and an insulating layer 226 are formed on a substrate 1000B. The substrate 1000B may include semiconductor elements such as Si and / or Ge. As another example, the substrate 1000B can include compound semiconductors such as SiC, GaAs, InAs, and InP.

[0077] An etch stop layer 222 is formed on the top surface of the substrate 1000B. The etch stop film 222 may include, for example, silicon oxide. A plurality of sacrificial layers 224 and a plurality of insulating layers 226 are alternately stacked on the etch stop film 222 in a repeated manner. The thickness of the top insulating layer 226 is greater than the thickness of the other insulating layers 226 . The insulating layer 226 may include, for example, silicon dioxide. The sacrificial layer 224 has a different etch selectivity than the etch stop layer 222 and the insulating layer 226 . The sacrificial layer 224 may include, for example, a silicon nitride film, a silicon oxynitride film, a polysilicon film, or a polysilicon germanium film.

[0078] Referring to FIG. 5B, a channel hole 230 is formed to penetrate the insulating layer 226, the sacrificial layer 224, and the etch stop layer 222. The channel hole 230 exposes the substrate 1000B.

[0079] Referring to FIG. 5C, a charge storage pattern 232 , a tunnel insulating pattern 234 , a semiconductor pattern 240 , and a buried insulating layer 242 are formed in each channel hole 230 . The charge storage pattern 232 covers the inner wall of each channel hole 230 . The charge storage pattern 232 may include, for example, a silicon nitride film. A tunnel insulating pattern 234 is formed on the sidewall of the charge storage pattern 232 within each channel hole 230 . The tunnel insulating pattern 234 may include, for example, a silicon oxide film. A semiconductor pattern 240 is formed in each channel hole 230 to cover the sidewalls of the tunnel insulating pattern 234 and the top surface of the substrate 1000B. The semiconductor pattern 240 serves as a channel region. A buried insulating layer 242 is formed on the semiconductor pattern 240 to fill each of the channel holes 230 . The buried insulating film 242 may be formed of, for example, a high density plasma oxide film, an SOG (Spin On Glass) film, and / or a CVD oxide film. The charge storage pattern 232 , the tunnel insulating pattern 234 , the semiconductor pattern 240 , and the buried insulating layer 242 may be localized within each channel hole 230 .

[0080] The conductive pads 250 are formed on the upper portions of the channel holes 230, respectively. Each of the conductive pads 250 is formed on the charge storage pattern 232 , the tunnel insulating pattern 234 , the semiconductor pattern 240 , and the buried insulating layer 242 . The conductive pad 250 may be made of a conductive material such as a metal or a semiconductor material doped with impurities. The lower surface of the conductive pad 250 is disposed at a level higher than the upper surface of the top sacrificial layer 224 . The conductive pad 250 functions as a drain region. Although not shown, a capping film may be further formed on the top insulating layer 226 and the conductive pads 250 . The capping film may include an insulating material.

[0081] Referring to FIG. 5D, an opening 260 is formed through the insulating layer 226, the sacrificial layer 224, and the etch stop layer 222. Opening 260 exposes substrate 1000B. Each of the openings 260 is a word line cut region.

[0082] Referring to FIG. 5E, the sacrificial layer 224 exposed at the opening 260 is removed to form the gate region GS. The removal of the sacrificial layer 224 is carried out by an etching process. Gate regions GS are provided between the etch stop layer 222 and the bottom insulating layer 226, and between the insulating layers 226, respectively. The gate region GS is an empty space. The gate region GS may be connected to at least one of the openings 260 . The gate region GS exposes the charge storage pattern 232 .

[0083] Referring to FIG. 5F, a blocking insulating film 2000B is formed to cover the inner wall of the gate region GS. Blocking insulating film 2000B comprises an aluminum-containing film of the present invention. The blocking insulating film 2000B can be formed by the thin film forming method previously described with reference to FIGS. 1, 2, 3A, and 3B. For example, the blocking insulating film 2000B is formed by a vapor deposition process using a vapor deposition precursor containing an aluminum compound. The deposition process is an atomic layer deposition (ALD) process. The deposition precursors are delivered through opening 260 .

[0084] The aluminum compound according to the embodiment of the present invention has thermal stability, and can form the blocking insulating film 2000B with a small thickness. For example, the blocking insulating film 2000B is a single thin film having a thickness of 0.05 Å to 0.6 Å. As another example, the blocking insulating layer 2000B may include a plurality of thin films, each of which may have a thickness of 0.05 Å to 0.6 Å. The blocking insulating film 2000B exhibits excellent properties. The deposition process is carried out at a temperature of 300°C to 600°C. The formation of the blocking insulating film 2000B may further include a step of annealing at 500°C to 1150°C. The annealing process can densify the blocking insulating film 2000B.

[0085] Referring to FIG. 5G, a gate conductive layer 264P is formed on the blocking insulating layer 2000B. The gate conductive film 264P fills the gate region GS. The gate conductive film 264P may include a first conductive barrier film and a first conductive film. The first conductive barrier film may comprise a conductive metal nitride film, such as TiN or TaN. The first conductive barrier film is in physical contact with the blocking insulating film 2000B. The first conductive film may include conductive polysilicon, a metal, a metal silicide, or a combination thereof.

[0086] Referring to FIG. 5H, the gate conductive layer 264P and the blocking insulating layer 2000B are patterned to form a gate electrode 264 and a blocking insulating pattern 2000B', respectively. The patterning of the gate conductive film 264P and the blocking insulating film 2000B is performed by an etching process. The patterning of the gate conductive layer 264P and the blocking insulating layer 2000B can be performed in a single step. Etching of the gate conductive film 264P and the blocking insulating film 2000B is performed until the sidewalls of the insulating layer 226 and the top surface of the substrate 1000B are exposed. Thus, the gate electrode 264 and the blocking insulating pattern 2000B' are formed.

[0087] The aluminum compounds according to embodiments of the present invention may contain no impurities or very low levels of impurities. Therefore, the blocking insulating pattern 2000B' may include an aluminum oxide film that is free of impurities or has a very low concentration of impurities. Impurities are, for example, carbon residues. As described in FIG. 5F, the annealing process densifies the blocking insulating layer 2000B, thereby preventing over-etching of the blocking insulating layer 2000B during etching of the blocking insulating layer 2000B and the gate conductive layer 264P in FIG. 5H. After forming the gate electrode 264 and the blocking insulating pattern 2000B', impurities are implanted into the exposed substrate 1000B. Thus, a common source region 268 is formed in the substrate 1000B.

[0088] Referring to FIG. 5I, insulating spacers 272 are formed within the openings 260, respectively. An insulating spacer 272 covers the interior sidewall of the opening 260 . An insulating spacer 272 exposes the common source region 268 . The insulating spacers 272 may include a silicon-based insulating material. Conductive plugs 274 are formed in each opening 260 . A conductive plug 274 is formed on the sidewall of the insulating spacer 272 to fill the opening 260 . The conductive plugs 274 each connect to the common source region 268 .

[0089] The conductive plug 274 may include a second conductive barrier film and a second conductive film. The second conductive barrier films are each in physical contact with a corresponding insulating spacer 272 . The second conductive barrier film may comprise a conductive metal nitride film, such as TiN or TaN. A second conductive film is provided on the second conductive barrier film, filling the opening 260 . The second conductive film may be made of a metal, such as tungsten.

[0090] First contacts 282 are formed on the conductive plugs 274, respectively. A first conductive layer 284 is formed on each of the first contacts 282 . The first contact 282 and the first conductive layer 284 may be made of a metal, a metal nitride, or a combination thereof. The second contacts 292 are formed on the conductive pads 250 and connected to the conductive pads 250, respectively. A bit line 294 is formed on and connects to the second contact 292 . The second contact 292 and the bit line 294 can be made of metal, metal nitride, or a combination thereof. The manufacturing of the semiconductor device 200 is completed by the manufacturing example described above. The semiconductor device 200 is a non-volatile memory device.

[0091] 6A to 6D are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to still another embodiment of the present invention. Referring to FIG. 6A, a conductive pattern 312 is formed on a substrate 1000C. The conductive pattern 312 is a source / drain region, a gate electrode, or a wiring layer. The conductive pattern 312 may include a metal or a doped semiconductor material. An interlayer insulating film pattern 314 is formed on the substrate 1000C. The interlayer insulating film pattern 314 has a hole 314H. The hole 314H exposes at least a portion of the conductive pattern 312. The interlayer insulating film pattern 314 may include a silicon-based insulating material.

[0092] Referring to FIG. 6B, a conductive barrier film 2000C is formed in the hole 314H. The conductive barrier film 2000C conformally covers the upper surface of the conductive pattern 312 exposed through the hole 314H and the upper and inner surfaces of the interlayer insulating film pattern 314. The conductive barrier film 2000C may include an aluminum nitride film. The conductive barrier film 2000C can be formed by the thin film formation method previously described with reference to FIGS. 1, 2, 3A, and 3B. The conductive barrier film 2000C is formed by a deposition process using an aluminum compound according to an embodiment of the present invention. The deposition process is an atomic layer deposition (ALD) process. The aluminum compound has thermal stability, and the conductive barrier film 2000C can be formed to a small thickness. For example, the conductive barrier film 2000C is a single thin film having a thickness of 0.05 Å to 0.6 Å. As another example, the conductive barrier film 2000C may include multiple thin films, each having a thickness of 0.05 Å to 0.6 Å. The conductive barrier film 2000C exhibits excellent properties.

[0093] Referring to FIG. 6C, an interconnect layer 330 is formed on the conductive barrier film 2000C to fill the holes 314H. The upper surface of the wiring layer 330 is located at a higher level than the upper surface of the interlayer insulating film pattern 314 . The wiring layer 330 may be made of a metal, such as tungsten or copper.

[0094] Referring to FIG. 6D, the wiring layer 330 is planarized to form a wiring pattern 331. Planarization of the wiring layer 330 can be performed by an etch-back or chemical mechanical polishing process. During the planarization process of the wiring layer 330, a portion of the conductive barrier film 2000C is also removed, forming a conductive barrier pattern 2000C'. A portion of the conductive barrier film 2000C is provided on the upper surface of the interlayer insulating film pattern 314. The wiring layer 330 is planarized until the upper surface of the interlayer insulating film pattern 314 is exposed. The wiring pattern 331 and the conductive barrier pattern 2000C' are localized within the hole 314H. Thus, the fabrication of the semiconductor device 300 is completed. The thin thickness of the conductive barrier pattern 2000C' allows for high integration and miniaturization of the semiconductor device 300.

[0095] Figure 7A is a plan view showing a partial schematic configuration of a semiconductor element according to an embodiment of the present invention, Figure 7B is a schematic oblique view of the semiconductor element of Figure 7A, and Figure 7C is a schematic cross-sectional view for explaining a manufacturing method of a semiconductor element according to an embodiment of the present invention, which is a cross-section taken along lines II' and II-II' of Figure 7A.

[0096] 7A to 7C, a semiconductor device 400 includes a substrate 1000D, an isolation layer 402, and a gate structure 420. The semiconductor element 400 is a transistor. The substrate 1000D has a protruded fin portion F. The fin portion F extends along a first direction D1. The first direction D1 is parallel to the bottom surface of the substrate 1000D. The element isolation film 402 is formed on the substrate 1000D and covers the lower sidewall of the fin portion F. The isolation film 402 may include a silicon oxide film, a silicon nitride film, a silicon oxynitride film, or a combination thereof. The element isolation film 402 exposes the upper portion of the fin portion F.

[0097] A gate structure 420 is formed on the substrate 1000D and across the fin portion F. The gate structure 420 extends in a second direction D2. The second direction D2 is parallel to the lower surface of the substrate 1000D and intersects with the first direction D1. Source / drain regions 430 are formed on either side of the fin portion F. The source / drain regions 430 can be formed by performing a selective epitaxial growth process using the fin portion F as a seed. The source / drain regions 430 may include silicon, silicon germanium, and / or silicon carbide. The source / drain regions 430 may have a variety of shapes.

[0098] As shown in FIG. 7C, the gate structure 420 includes a stacked interface layer 412, a high dielectric film 414, and a gate electrode pattern 420G. An interface layer 412 is provided on the top surface of the fin portion F. The interface layer 412 may include a silicon-based insulating material, such as an oxide, a nitride, or an oxynitride. The high dielectric constant film 414 has a higher dielectric constant than that of a silicon oxide film. For example, the high dielectric constant film 414 has a dielectric constant of about 10-25. The high dielectric film 414 may include a metal oxide or a metal oxynitride.

[0099] The gate electrode pattern 420G may include a first metal-containing layer 426A, a second metal-containing layer 426B, and a gap-fill metal layer 428. The first metal-containing layer 426A may include a P-type work function conductive material, such as TiN. The second metal-containing layer 426B may include an N-type work function conductive material, such as an aluminide containing Ti or Ta. As another example, the second metal-containing layer 426B can include an aluminum compound that includes carbon atoms. In this case, the second metal-containing layer 426B may include TiAlC, TiAlCN, TaAlC, TaAlCN, or a combination thereof. As another example, the second metal-containing layer 426B can include TiAl, TiAlN, TaAlN, or a combination thereof.

[0100] The first metal-containing layer 426A and the second metal-containing layer 426B can adjust the work function of the gate structure 420. Thus, the threshold voltage of the gate structure 420 can be adjusted. Second metal-containing layer 426B can be formed by the thin film formation method previously described with reference to FIGS. 1, 2, 3A, and 3B. For example, second metal-containing layer 426B can be formed by a vapor deposition process using a vapor deposition precursor that includes an aluminum compound of the present invention. The deposition process is an atomic layer deposition (ALD) process. The aluminum compound has thermal stability, allowing the second metal-containing layer 426B to be formed with a small thickness. For example, the second metal-containing layer 426B is a single thin film having a thickness of 0.05 Å to 0.6 Å. As another example, the second metal-containing layer 426B may include a plurality of thin films, each having a thickness of 0.05 Å to 0.6 Å. The second metal-containing layer 426B exhibits excellent properties.

[0101] A gap-fill metal layer 428 is provided on the second metal-containing layer 426B. The gap-fill metal layer 428 may include, for example, aluminum, tungsten (W), metal nitrides (e.g., TiN and / or TaN), metal carbides, metal suicides, metal aluminum carbides, metal aluminum nitrides, and / or metal silicon nitrides. The gate structure 420 may be formed by a replacement metal gate (RMG) process. Insulating spacers 442 are formed on either side of the gate structure 420 . An interlayer insulating film 444 is formed on the source / drain regions 430 . An interlayer insulating film 444 covers the sidewalls of the insulating spacers 442 . The interlayer insulating film 444 may include a silicon-based insulating material. The manufacturing of the semiconductor device 400 is completed by the manufacturing example described above. The semiconductor element 400 is a transistor. The thin second metal-containing layer 426B allows the semiconductor device 400 to be highly integrated and miniaturized.

[0102] Hereinafter, the aluminum compound of the present invention (the numbers are those of the compound group A) and a method for forming a thin film using the same will be described with reference to examples and comparative examples of the present invention. In the present examples and comparative examples, elemental analysis is carried out using an inductively coupled plasma atomic emission spectrometer (ICP-AES). In this example and comparative example, nuclear magnetic resonance analysis was carried out using deuterium-substituted benzene as a solvent. The results of nuclear magnetic resonance analysis are shown as (chemical shift: multiplicity: number of H). In the present examples and comparative examples, thermal analysis was carried out using a thermogravimetry and differential thermal analysis (TG-DTA) apparatus. At this time, argon gas is supplied at a rate of 100 mL / min. The temperature rise rate is 10°C / min. When the mass of the sample supplied to the apparatus became 50 wt% of the mass initially supplied, the temperature (hereinafter referred to as the 50 wt% reduction temperature) was measured.

[0103] Example 1: Preparation of Aluminum Compound No. 2 "Trimethyl aluminum" was dissolved in toluene to prepare a "Trimethyl aluminum / Toluene" solution. To a 50 mL three-neck flask were added 8.09 mL (14.6 mmol) of the "Trimethyl Aluminum / Toluene" solution and 10 mL of dehydrated toluene. Thereafter, the "Trimethyl Aluminum / Toluene" solution was cooled to 0°C, and 2.25 g (14.6 mmol) of "N,N'-Diethyl-2,4-pentanediimine" was added to prepare a mixed solution. The mixture was stirred at 0° C. for 3 hours, and then the solvent was distilled off from the mixture to give 2.20 g of a product (yield 72%). [Elemental analysis] Al: 12.5 wt% (theoretical value: 12.8%) C: 63.1 wt%, H: 11.5 wt%, N: 12.8 wt% (theoretical values: C: 62.8%, H: 11.0%, N: 13.3%) [Nuclear magnetic resonance ( 1 H-NMR) analysis] (4.40:s:1H)(3.04:q:4H)(1.53:s:6H)(0.95:t:6H)(-0.29:s:6H) [Thermal analysis] Using a 9.614 mg sample, the 50 wt% reduction temperature was determined to be 174°C.

[0104] Example 2: Preparation of Aluminum Compound No. 3 To a 200 mL four-neck flask were added 33.1 mL (59.6 mmol) of the "Trimethyl Aluminum / Toluene" solution and 25 mL of dehydrated toluene. Thereafter, the "Trimethyl Aluminum / Toluene" solution was cooled to 0°C, and 10.9 g (59.6 mmol) of "N,N'-Diisopropyl-2,4-pentanediimine" was added to prepare a mixed solution. The mixture was stirred at room temperature (25°C) for 5 hours. The solvent was distilled off from the mixture to give 12.0 g of a product (yield 84%). [Elemental analysis] Al: 11.7 wt% (theoretical value 11.3%) C: 65.2 wt%, H: 11.7 wt%, N: 11.4 wt% (theoretical values: C: 65.5%, H: 11.4%, N: 11.8%) [Nuclear magnetic resonance ( 1 H-NMR) analysis] (4.41:s:1H)(3.54:sep:2H)(1.60:s:6H)(1.20:d:12H)(-0.18:s:6H) [Thermal analysis] Using a 10.197 mg sample, the 50 wt% reduction temperature was measured to be 188°C.

[0105] Example 3: Preparation of Aluminum Compound No. 5 To a 300 mL four-neck flask were added 81 mL (146 mmol) of "Trimethyl Aluminum / Toluene" solution and 80 mL of dehydrated toluene. The solution was stirred and cooled to 0°C. To the solution, 26.6 g (146 mmol) of "N,N'-Diethyl-3,5-heptanediimine" was added to prepare a mixed solution. The mixture was heated to 60°C and then stirred at 60°C for 4 hours. The solvent was distilled off from the mixture to give 28.9 g of product (yield 83%). [Elemental analysis] Al: 11.1 wt% (theoretical value: 11.3%) C: 65.8 wt%, H: 11.3 wt%, N: 11.8 wt% (theoretical values: C: 65.5%, H: 11.4%, N: 11.8%) [Nuclear magnetic resonance ( 1 H-NMR) analysis] (0.90:s:1H)(3.11:q:4H)(1.91:q:4H)(1.01:t:6H)(0.91:t:6H)(-0.29:s:6H) [Thermal analysis] Using a 9.456 mg sample, the 50 wt% reduction temperature was determined to be 181°C.

[0106] Example 4: Preparation of Aluminum Compound No. 7 To a 300 mL four-neck flask was added 46 mL (83.2 mmol) of "Trimethyl Aluminum / Toluene" solution, and the solution was cooled to 20°C. To the cooled solution, 19.8 g (83.2 mmol) of "N,N'-Di-sec-butyl-3,5-heptanediimine" was added to prepare a mixed solution. The mixture was stirred at room temperature (25°C) for 5 hours. The solvent was distilled off from the mixture to give 12.9 g of product (yield 53%). [Elemental analysis] Al: 9.6 wt% (theoretical value 9.2%) C: 68.5 wt%, H: 12.4 wt%, N: 9.5 wt% (theoretical values: C: 69.3%, H: 12.0%, N: 9.5%) [Nuclear magnetic resonance ( 1 H-NMR) analysis] (4.56:s:1H)(3.33:sext:2H)(2.02:qt:4H)(1.67:m:4H)(1.27:t:6H)(0.95:t:6H)(0.80:td:6H)(-0.232:t:6H) [Thermal analysis] Using a 9.986 mg sample, the 50 wt% reduction temperature was determined to be 208°C.

[0107] Example 5: Preparation of Aluminum Compound No. 19 A first solution was prepared by adding 14.3 g (107 mmol) of aluminum chloride and 200 mL of dehydrated toluene to a 100 mL three-neck flask and stirring the mixture. The first solution was cooled to 10°C. A 500 mL three-neck flask was prepared, and 20.1 g (107 mmol) of "N,N'-Diethyl-3,5-heptanediimine" and 200 mL of dehydrated toluene were added thereto and stirred to prepare a second solution. The second solution was cooled to 0°C. To the cooled second solution, 65.2 mL (107 mmol) of a solution of n-butyllithium dissolved in n-hexane was added dropwise. Thereafter, the second solution was warmed to room temperature (25°C) and stirred for 2 hours. The first solution was added dropwise to the second solution, and the mixture was stirred at room temperature for 5 hours to prepare a mixed solution. The mixture was filtered, the solvent was distilled off, and the mixture was purified to obtain 15.3 g of an intermediate (aluminum compound No. 47). 1.89 g (6.77 mmol) of the intermediate and 50 mL of dehydrated toluene were added to a three-necked flask, stirred, and cooled to -30°C. To the intermediate was added 19.3 mL (13.5 mmol) of a solution of isopropyl lithium dissolved in n-pentane. The intermediate was then stirred at room temperature for 3 hours to give the product. The product was filtered and the solvent was evaporated to give 0.78 g (39% yield) of the final product. [Elemental analysis] Al: 8.6 wt% (theoretical value: 9.2%) C: 70.5 wt%, H: 11.7 wt%, N: 9.2 wt% (theoretical values: C: 69.3%, H: 12.0%, N: 9.5%) [Nuclear magnetic resonance ( 1 H-NMR) analysis] (4.37:s:1H)(3.07:q:4H)(1.91:q:4H)(1.46:d:12H)(1.01:t:6H)(0.94:t:6H)(0.58:sep:2H) [Thermal analysis] Using a 10.371 mg sample, the 50 wt% reduction temperature was determined to be 214°C.

[0108] Example 6: Preparation of Aluminum Compound No. 26 A first solution was prepared by adding 14.3 g (107 mmol) of aluminum chloride and 200 mL of dehydrated toluene to a 100 mL three-neck flask and stirring the mixture. The solution was cooled to 10°C. A 500 mL three-neck flask was prepared separately, and 20.1 g (107 mmol) of "N,N'-Diethyl-3,5-heptanediimine" and 200 mL of dehydrated toluene were added and stirred to prepare a second solution. The second solution was cooled to 0°C. To the cooled second solution, 65.2 mL (107 mmol) of a solution of n-butyllithium dissolved in n-hexane was added dropwise. The second solution was allowed to warm to room temperature and stirred at room temperature for 2 hours. The first solution was added dropwise to the second solution to prepare a mixed solution. The mixture was stirred at room temperature for 5 hours. The mixture was filtered, the solvent was distilled off, and the residue was purified to obtain 15.3 g of an intermediate (compound No. 47). 0.973 g (3.49 mmol) of the intermediate and 50 mL of dehydrated toluene were added to a three-necked flask and stirred. Isopropylmagnesium chloride was dissolved in tetrahydrofuran (THF) to prepare an isopropanol magnesium chloride solution. To the intermediate solution was added 3.5 mL (3.49 mmol) of isopropanol magnesium chloride solution. The intermediate solution was heated to 70° C. and stirred for 5 hours to give the product. The solvent was evaporated from the product to give 0.54 g (54% yield) of the final product. [Elemental analysis] Al: 8.9 wt% (theoretical value: 9.4%) C: 57.9 wt%, H: 10.8 wt%, N: 10.4 wt%, Cl: 11.5 wt% (theoretical values: C: 58.6%, H: 9.8%, N: 9.8%, Cl: 12.4%) [Nuclear magnetic resonance ( 1 H-NMR) analysis] (4.47:s:1H)(3.18:qdd:4H)(1.86:qdd:4H)(1.41:t:6H)(1.08:t:6H)(0.85:td:6H)(0.66:m:1H) [Thermal analysis] Using a 10.005 mg sample, the 50 wt% reduction temperature was determined to be 224°C.

[0109] Example 7: Preparation of Aluminum Compound No. 27 A first solution was prepared by adding 8.68 g (65.1 mmol) of aluminum chloride and 100 mL of dehydrated toluene to a 500 mL four-neck flask. A 200 mL four-neck flask was prepared separately, and 13.7 g (65.1 mmol) of "N,N'-Diiopropyl-3,5-heptanediimine" and 100 mL of dehydrated toluene were added thereto and stirred to prepare a second solution. The second solution was cooled to 30°C. To the cooled second solution, 42 mL of a solution of n-butyllithium dissolved in n-hexane was added dropwise. The second solution was warmed to room temperature and then stirred for 2 hours. The first solution was added dropwise to the second solution to prepare a mixed solution. The mixture was stirred at room temperature for 18 hours. The mixture was filtered, the solvent was distilled off, and the residue was purified to obtain 15.9 g of an intermediate (compound No. 48). 1.72 g (5.60 mmol) of the intermediate and 50 mL of dehydrated toluene were added to a three-neck flask and stirred. The intermediate was cooled to -20°C. Isopropylmagnesium chloride was dissolved in tetrahydrofuran (THF) to prepare an isopropanol magnesium chloride solution. To the intermediate solution was added 5.60 mL (5.60 mmol) of isopropanol magnesium chloride solution. The intermediate solution was heated to 70° C. and stirred for 22 hours to give the product. The solvent was evaporated from the product to give 0.70 g (40% yield) of the final product. [Elemental analysis] Al: 8.0 wt% (theoretical value: 8.6%) C: 62.0 wt%, H: 9.8 wt%, N: 8.2 wt%, Cl: 12.0 wt% (theoretical values: C: 61.0%, H: 10.2%, N: 8.9%, Cl: 11.3%) [Nuclear magnetic resonance ( 1 H-NMR) analysis] (4.45:s:1H)(3.63:m:2H)(1.93:m:4H)(1.49:d:6H)(1.38:d:6H)(1.32:d:6H)(0.87:t:6H)(0.55:sep:1H) [Thermal analysis] Using a 9.601 mg sample, the 50 wt% reduction temperature was determined to be 222°C.

[0110] Example 8: Preparation of Aluminum Compound No. 33 26.7 g (200 mmol) of aluminum chloride and 150 mL of dehydrated toluene were added to a 1 L four-neck flask and stirred to prepare a first solution. The first solution was cooled to 20°C. A "lithium dimethylamide" solution was prepared by dissolving 30.6 g (600 mmol) of "lithium dimethylamide" in a dehydrated toluene solvent. 300 mL of the "LithiumDimethylamide" solution was added dropwise to the cooled first solution to prepare a mixed solution. The mixture was heated to 50° C. and stirred for 7 hours. The mixture was filtered and the solvent was distilled off to obtain 30.6 g of an intermediate. In a 200 mL four-neck flask, 4.86 g (15.2 mmol) of the intermediate and 100 mL of dehydrated toluene were added and stirred. Thereafter, 5.54 g (30.4 mmol) of "N,N'-Diethyl-3,5-heptanediimine" was further added to the flask and stirred to obtain a product. Stirring was carried out at 100° C. for 12 hours. The solvent was evaporated from the product to give 4.27 g (47% yield) of the final product. [Elemental analysis] Al: 9.8 wt% (theoretical value: 9.1%) C: 59.2 wt%, H: 11.5 wt%, N: 19.5 wt% (theoretical values: C: 60.8%, H: 11.2%, N: 18.9%) [Nuclear magnetic resonance ( 1 H-NMR) analysis] (4.47s:1H)(3.24:q:4H)(2.89:s:12H)(1.96:q:4H)(1.08:t:6H)(0.94:t:6H) [Thermal analysis] Using a 9.936 mg sample, the 50 wt% reduction temperature was determined to be 205°C.

[0111] Example 9: Preparation of Aluminum Compound No. 34 A first solution was prepared by adding 8.68 g (65.1 mmol) of aluminum chloride and 100 mL of dehydrated toluene to a 500 mL four-neck flask and stirring the mixture. A second solution was prepared by adding 13.7 g (65.1 mmol) of "N,N'-Diiopropyl-3,5-heptanediimine" and 100 mL of dehydrated toluene to a 200 mL four-neck flask and stirring the mixture. The second solution was cooled to -30°C, and 42 mL of a solution of "N-butyllithium" dissolved in "n-hexane" was added dropwise thereto. The mixture was then heated to room temperature and stirred for 2 hours. The first solution was added to the second solution to form a mixed solution. The mixture was stirred at room temperature for 18 hours. The mixture was filtered, the solvent was distilled off, and the residue was purified to obtain 15.8 g of an intermediate (compound No. 48). 1.89 g (6.16 mmol) of the intermediate and 10 mL of dehydrated toluene were added to a three-necked flask and stirred. Thereafter, the intermediate was cooled to -20°C. A "lithium dimethylamide" solution was prepared by dissolving 30.6 g (600 mmol) of "lithium dimethylamide" in a dehydrated toluene solvent. 15 mL of "LithiumDimethylamide" solution was added to the intermediate to prepare an intermediate solution. The intermediate solution was allowed to warm to room temperature and stirred for 6 hours to give the product. The product was filtered. The solvent was evaporated from the product to give 1.34 g (67% yield) of the final product. [Elemental analysis] Al: 9.0 wt% (theoretical value: 8.3%) C: 62.2 wt%, H: 10.2 wt%, N: 18.6 wt% (theoretical values: C: 62.9%, H: 11.5%, N: 17.3%) [Nuclear magnetic resonance ( 1 H-NMR) analysis] (4.43:s:1H)(3.72:sep:2H)(2.75:s:12H)(2.04:q:4H)(1.30:d:12H)(0.98:t:6H) [Thermal analysis] Using a 9.976 mg sample, the 50 wt% reduction temperature was measured to be 214°C.

[0112] Example 10: Preparation of Aluminum Compound No. 40 A first solution was prepared by adding 14.3 g (107 mmol) of aluminum chloride and 200 mL of dehydrated toluene to a 500 mL four-neck flask and stirring the mixture. The first solution was cooled to 10°C. A second solution was prepared by adding 20.1 g (107 mmol) of "N,N'-Diethyl-3,5-heptanediimine" and 200 mL of dehydrated toluene to a 500 mL three-neck flask and stirring the mixture. The second solution was cooled to 0°C. 65.2 mL (107 mmol) of a solution of "N-butyllithium" dissolved in "n-hexane" was added dropwise to the second solution. The second solution was warmed to room temperature and stirred for 2 hours. The first solution was added dropwise to the second solution to prepare a mixed solution. The mixture was stirred at room temperature for 5 hours. The mixture was filtered, the solvent was distilled off, and the residue was purified to obtain 15.3 g of an intermediate (Compound No. 47). 1.21 g (4.33 mmol) of the intermediate and 10 mL of dehydrated toluene were added to a 50 mL three-neck flask and stirred to prepare an intermediate solution. The intermediate solution was cooled to -20°C. A "lithium dimethylamide" solution was prepared by dissolving 0.221 g (4.33 mmol) of "lithium dimethylamide" in a dehydrated toluene solvent. 10 mL of "LithiumDimethylamide" solution was added dropwise to the intermediate solution, and the mixture was stirred at room temperature for 5 hours to obtain a product. The product was filtered. The solvent was evaporated from the product to give 0.25 g (20% yield) of the final product. [Elemental analysis] Al: 10.2 wt% (theoretical value 9.4%) C: 55.3 wt%, H: 8.5 wt%, N: 13.5 wt%, Cl: 12.5 wt% (theoretical values: C: 54.3%, H: 9.5%, N: 14.6%, Cl: 12.3%) [Nuclear magnetic resonance ( 1 H-NMR) analysis] (4.51:s:1H)(3.27:qd:4H)(2.86:s:6H)(1.89:q:d:4H)(1.10:t:6H)(0.86:t:6H) [Thermal analysis] Using a 10.389 mg sample, the 50 wt% reduction temperature was determined to be 220°C.

[0113] Example 11: Preparation of Aluminum Compound No. 55 To a 300 mL four-neck flask were added 53.9 mL (97.1 mmol) of the "Trimethyl Aluminum / Toluene" solution and 50 mL of dehydrated toluene, and the solution was cooled to 10°C. To the cooled solution, 16.4 g (97.1 mmol) of "N-Isopropyl-5-imino-3-heptanone" was added to prepare a mixed solution. The mixture was allowed to warm to room temperature and then stirred for 6 hours. The mixture was evaporated to remove the solvent, yielding 19.5 g of the final product (89% yield). [Elemental analysis] Al: 11.2 wt% (theoretical value: 12.0%) C:64.7wt%, H:9.7wt%, N:5.5wt% (theoretical value; C:64.0%, H:10.7%, N:6.2%) [Nuclear magnetic resonance ( 1 H-NMR) analysis] (4.77:s:1H)(3.43:sep:1H)(2.07:q:2H)(1.71:q:2H)(1.09:d:6H)(1.04:t:3H)(0.72:t:3H)(-0.21:s:6H) [Thermal analysis] Using a 9.953 mg sample, the 50 wt% reduction temperature was determined to be 175°C.

[0114] Example 12: Preparation of Aluminum Compound No. 69 A first solution was prepared by adding 11.9 g (89.3 mmol) of aluminum chloride and 100 mL of dehydrated toluene to a 300 mL four-neck flask and stirring the mixture. The first solution was cooled to 0°C. A second solution was prepared by adding 11.4 g (89.3 mmol) of "N-Ethyl-4-imino-2-pentanone" and 100 mL of dehydrated toluene to a 200 mL four-neck flask and stirring the mixture. The second solution was cooled to -40°C. To the second solution, 57.4 mL (89.36 mmol) of "N-butyllithium solution" dissolved in "n-hexane" was added dropwise. The second solution was warmed to room temperature and then stirred for 2 hours. The first solution was added dropwise to the second solution to prepare a mixed solution. The mixture was allowed to warm to room temperature and then stirred for 20 hours. The mixture was filtered, and the solvent was purified by distillation to obtain 10.2 g of an intermediate. 1.59 g (7.10 mmol) of the intermediate and 50 mL of toluene were added to a three-necked flask and stirred to prepare an intermediate solution. The intermediate solution was cooled to -20°C. To the cooled intermediate solution was added dropwise 14.2 mL (7.10 mmol) of isopropanol magnesium chloride. The intermediate solution was heated to 50°C and stirred for 4 hours to give the product. The product was filtered. The solvent was removed from the product by evaporation to give 0.65 g (38% yield) of the final product. [Elemental analysis] Al: 12.2 wt% (theoretical value: 11.3%) C: 64.2 wt%, H: 12.0 wt%, N: 5.3 wt% (theoretical values: C: 65.2%, H: 11.0%, N: 5.9%) [Nuclear magnetic resonance ( 1 H-NMR) analysis] (4.56:s:1H)(2.87:q:2H)(1.72:s:3H)(1.46:dd:12H)(1.24:s:3H)(0.82:t:3H)(0.60:sep:2H) [Thermal analysis] Using a 10.228 mg sample, the 50 wt% reduction temperature was measured to be 177°C.

[0115] <Comparative Example 1> An aluminum compound represented by the following chemical formula 4A is prepared as a comparative example. [ka]

[0116] <Comparative Example 2> An aluminum compound represented by the following chemical formula 4B is prepared as a comparative example. [ka]

[0117] <Comparative Example 3> An aluminum compound represented by the following chemical formula 4C is prepared as a comparative example. [ka]

[0118] Table 1 below shows the results of evaluating the spontaneous combustion properties of the aluminum compounds of Examples and Comparative Examples. The spontaneous combustion property was determined by observing whether or not an aluminum compound ignites after being left in the air. [Table 1]

[0119] Referring to Table 1, the aluminum compound of Comparative Example 1 has pyrophoric properties. It is clear that the aluminum compound of Comparative Example 1 is unstable in the atmosphere and therefore difficult to use as a deposition precursor. The aluminum compounds of Examples 1 to 12 do not have spontaneous combustion properties. The aluminum compounds of Examples 1 to 12 can be used as vapor deposition precursors.

[0120] Table 2 below shows the results of measuring the melting points and thermal decomposition temperatures of Examples 1 to 12, Comparative Example 2, and Comparative Example 3. The melting point was observed under the conditions of 1013 Pa and 30°C. The thermal decomposition temperature was measured using a differential scanning calorimeter. [Table 2]

[0121] Referring to Table 2, Comparative Example 2 has a low thermal decomposition temperature. The thermal decomposition temperature of the aluminum compound of Comparative Example 2 is lower than 300°C. When the aluminum compound of Comparative Example 2 is used as a vapor deposition precursor, the vapor deposition process may be limited by its low thermal stability. For example, the deposition window (ALD window) may be narrow. The aluminum compounds of Examples 1 to 12 have a relatively high thermal decomposition temperature of 300°C to 600°C. The aluminum compounds of Examples 1 to 12 have excellent thermal stability. Therefore, when an aluminum compound is used as a vapor deposition precursor, the limitations on the vapor deposition process can be reduced. For example, the deposition process can be performed over a relatively wide deposition window.

[0122] The deposition precursor may be delivered in a liquid state. The higher the melting point of the vapor deposition precursor, the more difficult it may be to prepare the vapor deposition precursor in a liquid state. Comparative Example 3 has a high melting point. For example, the melting point of Comparative Example 3 is 80°C. Therefore, when the aluminum compound of Comparative Example 3 is used as a vapor deposition precursor, it may be difficult to transport the vapor deposition precursor. The aluminum compounds of Examples 1 to 12 have relatively low melting points (for example, melting points of 45° C. or lower). Therefore, when the aluminum compounds of Examples 1 to 12 are used as vapor deposition precursors, the vapor deposition precursors are easily transported.

[0123] FIG. 8 is a graph showing the results of the film thickness deposited per cycle as a function of temperature. The thin film deposition process was carried out using Comparative Example 1 and Example 3 as deposition precursors, respectively. The horizontal axis represents the substrate temperature. The thin film is deposited by performing an atomic layer deposition process, and the thickness of the thin film deposited per cycle represents the deposition rate. Referring to FIG. 8, the thickness (c) of the thin film deposited using Comparative Example 1 is greater than the thickness (e) of the thin film deposited using Example 3 under the same temperature conditions. The deposition process using the aluminum compound according to the embodiment has a low deposition rate, which can reduce the thickness of the deposited thin film. For example, when Example 3 is used as the deposition precursor, the thickness (e) of the thin film deposited per cycle is 0.05 Å to 0.6 Å.

[0124] The present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the technical scope of the present invention. [Explanation of symbols]

[0125] 1. Deposition system 10 chambers 20 Precursor Supply Unit 30 Reaction gas supply unit 100 Semiconductor element 112 Element isolation region 120 Interlayer insulating film 124 Conductive part 128, 226 insulating layer 130 Molded membrane 142 Sacrifice Pattern 144 Mask Pattern 150 Conductive film 170 Capacitor 1000, 1000A, 1000B, 1000C, 1000D board 2000 Thin Film 2000A Dielectric Film 2001 Deposition precursor 2100 precursor layer AC active area H1 Hall LE bottom electrode UE upper electrode

Claims

1. providing an atomic layer deposition precursor comprising an aluminum compound; and an atomic layer deposition step of forming a thin film using the deposition precursor, The aluminum compounds are represented by the following compound Nos. 5, 7, 19, 26, 27, 33, 34, 40, 55, and 69, In the atomic layer deposition step of forming the thin film, the thickness of the thin film deposited per cycle is 0.05 Å to 0.6 Å. 【Chemical 5(7)19(26)27(33)34(40)55(69)】

2. 2. The method of claim 1, wherein the aluminum compound has a thermal decomposition temperature of 300 to 600.degree.

3. The atomic layer deposition step of forming the thin film includes supplying the deposition precursor of atomic layer deposition into a chamber to form a precursor film on a substrate; 2. The method of claim 1, further comprising: supplying a reaction gas onto the precursor film.

4. supplying the reaction gas includes supplying the reaction gas into the chamber; In the step of supplying the deposition precursor, the temperature in the chamber is 300° C. to 600° C.; 4. The method of claim 3, wherein the temperature in the chamber is 300 to 600 degrees Celsius during the supplying of the reaction gas.

5. The atomic layer deposition step of forming the thin film is performed multiple times; 2. The method of claim 1, wherein the thin film comprises a plurality of thin films stacked together.

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