Aluminum compounds and methods for manufacturing semiconductor devices using them

Abstract

An aluminum compound and a method for manufacturing a semiconductor device using the aluminum compound are provided. The aluminum compound can be represented by Formula 1. [Formula 1]

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to Korean Patent Application No. 10-2018-0169699, filed on December 26, 2018, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] Exemplary embodiments of the present invention relate to aluminum compounds, methods for manufacturing semiconductor devices using said aluminum compounds, and deposition processes using said aluminum compounds. Background Technology

[0004] Due to advancements in electronic technology, the miniaturization of semiconductor devices has accelerated rapidly in recent years. Consequently, the structures that form the patterns in semiconductor devices are becoming increasingly complex and miniaturized. Therefore, there is a need to develop a raw material compound that can form films of uniform thickness in complex and minute three-dimensional structures by ensuring thermal stability during the formation of aluminum-containing films. Summary of the Invention

[0005] An exemplary embodiment of the present invention provides a deposition precursor with thermal stability and transportability.

[0006] An exemplary embodiment of the present invention provides a method for manufacturing a semiconductor device, the method comprising forming a thin film having a thin thickness and improved properties.

[0007] Exemplary embodiments of the present invention provide aluminum compounds and methods for manufacturing semiconductor devices using said aluminum compounds. An aluminum compound according to one aspect of the present invention can be represented by Formula 1.

[0008] [Formula 1]

[0009]

[0010] A method for manufacturing a semiconductor device according to one aspect of the present invention includes: preparing a deposition precursor comprising an aluminum compound; and forming a thin film using the deposition precursor, wherein the aluminum compound may be represented by Formula 1.

[0011] [Formula 1]

[0012] Attached Figure Description

[0013] The accompanying drawings are included to provide a further understanding of the inventive concept, and are incorporated in and constitute a part of this specification. These drawings illustrate exemplary embodiments of the inventive concept and, together with their description, serve to explain the principles of the inventive concept. In the drawings:

[0014] Figure 1 This is a diagram illustrating the deposition process using aluminum compounds according to an exemplary embodiment;

[0015] Figure 2 This is a schematic diagram illustrating a deposition system according to an exemplary embodiment;

[0016] Figure 3A and Figure 3B This is a diagram illustrating the formation of a thin film according to an exemplary embodiment;

[0017] Figures 4A to 4J This is a diagram illustrating a method for manufacturing a semiconductor device according to an exemplary embodiment;

[0018] Figures 5A to 5I This is a diagram illustrating a method for manufacturing a semiconductor device according to an exemplary embodiment;

[0019] Figures 6A to 6D This is a diagram illustrating a method for manufacturing a semiconductor device according to an exemplary embodiment;

[0020] Figure 7A This is a plan view illustrating a semiconductor device according to an exemplary embodiment;

[0021] Figure 7B It is shown Figure 7A A three-dimensional view of a semiconductor device;

[0022] Figure 7C It is along Figure 7A Cross-sectional views obtained from lines I-I' and II-II' in the diagram; and

[0023] Figure 8 The results show the thickness of the film deposited in each cycle, depending on the temperature. Detailed Implementation

[0024] In this disclosure, "substituted or unsubstituted" can mean substituted or unsubstituted by one or more substituents selected from the group consisting of: hydrogen atom, deuterium atom, halogen atom, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, hydroxyl, alkoxy, aryloxy, alkylthio, arylthio, cyano, halogen, carbonyl, amino, and derivatives thereof. Furthermore, each of the exemplified substituents can be substituted or unsubstituted. For example, methylamino can be understood as amino.

[0025] In this disclosure, the alkyl group can be a straight-chain alkyl group, a branched alkyl group, or a cyclic alkyl group. There is no particular limitation on the number of carbon atoms in the alkyl group, but it can be an alkyl group with 1 to 6 carbon atoms.

[0026] In this disclosure, the number of carbon atoms in the amine / amino group is not particularly limited, but can be from 1 to 6. The amine can include at least one selected from the group consisting of aliphatic amines with 1 to 6 carbon atoms and cyclic amines with 3 to 6 carbon atoms. The amino group can include alkylamino groups. Alkylamino groups can include monoalkylamino and dialkylamino groups.

[0027] In this disclosure, halogen atoms may include fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

[0028] Where a chemical bond is not drawn where it is required to be, unless otherwise defined in the chemical formula, it may represent a hydrogen bond bonded to that position. In this disclosure, room temperature may mean approximately 25°C.

[0029] In this disclosure, the same reference numerals throughout the entire disclosure may refer to the same constituent elements.

[0030] The following will describe an aluminum compound and a method for preparing said aluminum compound according to one aspect of the present invention.

[0031] According to one aspect of the present invention, an aluminum compound can be represented by the following formula 1.

[0032] [Formula 1]

[0033]

[0034] In Equation 1, R 1 and R 2 Each is independently selected from the group consisting of alkyl groups of 1 to 6 carbon atoms, dialkylamino groups of 2 to 6 carbon atoms, alkoxide groups of 1 to 6 carbon atoms, and halogen atoms, where Z is O or NR. 7 R 3 It is any one of the groups consisting of hydrogen, deuterium, and alkyl groups with 1 to 6 carbon atoms, R 4 and R 7 Each independently is selected from the group consisting of hydrogen, deuterium, alkyl groups of 1 to 6 carbon atoms and (dialkylamino)alkyl groups of 3 to 10 carbon atoms, and R 5 and R 6 Each is independently selected from the group consisting of hydrogen, deuterium, and alkyl groups with 1 to 6 carbon atoms.

[0035] In Equation 1, if R 1 R 2 R 3 R 4 R 5 R 6 and R 7If it is an alkyl group, then the number of carbon atoms in the alkyl group can be 1 to 6 or 1 to 4. The number of carbon atoms in a (dialkylamino)alkyl group can refer to the total number of carbon atoms in the (dialkylamino)alkyl group.

[0036] In Equation 1, if Z is NR 7 Then N can bond with Al.

[0037] In Formula 1, the alkyl group having 1 to 6 carbon atoms may include, for example, methyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, amyl, and / or isopentyl, as well as hexyl. However, embodiments of the present invention are not limited thereto.

[0038] Dialkylamino groups with 2 to 6 carbon atoms may include, for example, dimethylamino, diethylamino, dipropylamino, diisopropylamino, ethylmethylamino, propylmethylamino and / or isopropylmethylamino.

[0039] Alkoxides with 1 to 6 carbon atoms may include, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentoxy, isopentoxy, and / or tert-pentoxy.

[0040] Halogen atoms can include F, Cl and / or Br.

[0041] Alkyl groups with 3 to 10 carbon atoms may include, for example, dimethylaminomethyl, ethylmethylaminomethyl, diethylaminomethyl, dimethylaminoethyl, ethylmethylaminoethyl and / or diethylaminoethyl.

[0042] The aluminum compound represented by Formula 1 can be any one selected from compound group A.

[0043] [Compound Group A]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049] In compounds 1 through 85 of group A, Me is methyl, Et is ethyl, iPr is isopropyl, sBu is sec-butyl, tBu is tert-butyl, and DMA is dimethylamino.

[0050] iPr can be represented by the following equation 2A.

[0051] [Equation 2A]

[0052]

[0053] sBu can be represented by the following equation 2B.

[0054] [Formula 2B]

[0055]

[0056] tBu can be represented by the following equation 2C.

[0057] [Equation 2C]

[0058]

[0059] DMA can be represented by the following 2D formula.

[0060] [Form 2D]

[0061]

[0062] In formulas 2A to 2D, * refers to the junction with the corresponding one of C, N and O in compound group A from number 1 to number 85.

[0063] The aluminum compound can be used as a deposition precursor. For example, it can be used as a deposition precursor for atomic layer deposition or chemical vapor deposition (CVD). Improved stability (e.g., thermal stability) of the deposition precursor can enhance the properties of the deposited film.

[0064] According to exemplary embodiments, aluminum compounds can have aluminum-nitrogen (Al-N) bonds or aluminum-oxygen (Al-O) bonds (Al-Z bonds in Formula 1). When aluminum is directly bonded to nitrogen or oxygen, the bonding force between aluminum and other elements bonded to aluminum can be increased. That is, because of the provision of aluminum-nitrogen (Al-N) or aluminum-oxygen (Al-O) bonds, aluminum and R... 1 The bonding force between them and aluminum and R 2 The bonding forces between them can be increased. Therefore, aluminum compounds can exhibit excellent stability.

[0065] Aluminum compounds may contain a nitrogen at the 5-position as shown in Formula 3, and this nitrogen may contain a lone pair of electrons. The lone pair of nitrogen can interact with aluminum, as indicated by the dashed line. The interaction between aluminum and the nitrogen at the 5-position can be an intramolecular interaction. Due to this interaction, aluminum compounds can form a hexagonal ring structure. Compounds having this hexagonal ring structure can be stable. Therefore, the stability of aluminum compounds can be further improved.

[0066] [Formula 3]

[0067]

[0068] In Equation 3, R 1 R 2 R 3 R 4 R 5 R 6 And Z is the same as that defined in Equation 1.

[0069] Aluminum compounds can possess conjugated systems and form resonance structures. Therefore, the stability of aluminum compounds can be improved.

[0070] The stability of aluminum compounds can include thermal stability. For example, aluminum compounds can have high thermal decomposition temperatures. Aluminum compounds can have thermal decomposition temperatures ranging from about 300°C to about 600°C. When aluminum compounds are used as deposition precursors, the properties of the deposited film can be improved. The film can have high density. When the thermal decomposition temperature of the aluminum compound is below about 300°C, the properties of the deposited film may deteriorate, or the conditions of the deposition process may be limited.

[0071] When an aluminum compound is used as a deposition precursor, the deposition process can have a wider deposition window. The deposition window can refer to the temperature range used for the deposition process when using a certain deposition precursor. The deposition window can include an atomic layer deposition (ALD) window. The deposition process can be carried out at temperatures below the thermal decomposition temperature of the deposition precursor. According to an exemplary embodiment, the aluminum compound can have a high thermal decomposition temperature. When this aluminum compound is used as a deposition precursor, the deposition process can even be carried out at higher temperatures. Therefore, the limitations on the conditions of the deposition process can be reduced.

[0072] Aluminum compounds can have low melting points. The melting point of aluminum compounds can be, for example, from about -50°C to about 45°C. Aluminum compounds can be liquid at room temperature (e.g., about 25°C). The energy required to transport aluminum compounds in a liquid state can be low. Therefore, aluminum compounds can be easily transported in a liquid state.

[0073] Aluminum compounds may be free of impurities or may contain low concentrations of impurities. Impurities can refer to substances different from those represented by Formula 1. Impurities may include metallic impurities, halogenated impurities, and / or organic impurities.

[0074] The concentration of metallic impurities can be below about 1 ppm. The concentration of metallic impurities can be from about 0 to about 1 ppm. In this disclosure, the statement "the concentration of a certain impurity is about 0" can mean that no impurities are present. The concentration of metallic impurities can be below about 100 ppb. When the metallic impurities include multiple different metallic elements, the concentration of each metallic element can be below about 100 ppb, or below about 1 ppb. Metallic impurities can include alkali metals and / or alkaline earth metals. If the insulating layer contains metallic elements, the properties of the insulating layer may deteriorate.

[0075] Halogenated impurities may include fluorine, chlorine, and / or bromine. The concentration of halogenated impurities may be less than about 100 ppm. The concentration of halogenated impurities may be less than about 10 ppm or about 1 ppm.

[0076] The concentration of organic impurities can be below approximately 500 ppm. Alternatively, the concentration of organic impurities can be below approximately 500 ppm or below 10 ppm.

[0077] Aluminum compounds may be free of moisture or may contain a low concentration of moisture. The concentration of moisture (e.g., the concentration of H2O) in aluminum compounds may be less than about 100 ppm or less than about 1 ppm.

[0078] When the aluminum compound is in a liquid state, impurities can exist in particulate form. The content of impurity particles can be low. Impurity particles can have small diameters. If the diameter of the impurity particles is greater than about 0.3 μm, the number of impurity particles in about 1 ml of aluminum compound can be less than about 100. If the diameter of the impurity particles is greater than about 0.2 μm, the number of impurity particles in about 1 ml of aluminum compound can be less than about 100.

[0079] If the precursor contains impurities, contaminating particles may form in or on the deposited film. According to an exemplary embodiment, the aluminum compound may be impurity-free or may contain very low concentrations of impurities. Therefore, the deposited film can exhibit excellent properties.

[0080] The aluminum compound according to the exemplary embodiment may have a high vapor pressure or may be easily evaporated. The deposition process can be easily performed if a deposition precursor containing the aluminum compound is used.

[0081] Aluminum compounds can be prepared using diketimine or ketoimine compounds as reactants. Specific examples of aluminum compound preparation will be described in Experimental Examples 1 to 12.

[0082] The deposition process using aluminum compounds and the methods for forming thin films will be described below.

[0083] Figure 1 This is a diagram illustrating the deposition process using aluminum compounds according to an exemplary embodiment. Figure 2 This is a schematic diagram illustrating a deposition system according to an exemplary embodiment. Figure 3A and Figure 3B This is a diagram illustrating the formation of a thin film according to an exemplary embodiment.

[0084] Reference Figure 1 The deposition process may include: preparing a deposition precursor containing an aluminum compound (S10), supplying the deposition precursor to form a precursor layer (S20), and supplying a reactive gas to form a thin film (S30). The deposition process may also include performing a first venting process (S21) and a second venting process (S31). The deposition process may be an atomic layer deposition process.

[0085] Reference Figure 1 and Figure 2 The deposition system 1 may include a chamber 10, a precursor supply unit 20, and a reactive gas supply unit 30. The deposition system 1 can be used for an atomic layer deposition (ALD) process. Alternatively, the deposition system 1 can be used for a chemical vapor deposition process. A substrate 1000 can be loaded into the chamber 10. The substrate 1000 can be a wafer substrate, such as a semiconductor substrate.

[0086] A deposition precursor 2001 containing an aluminum compound can be prepared (S10). The deposition precursor 2001 can be conveyed and supplied to the precursor supply unit 20. The aluminum compound has a low melting point, and the deposition precursor 2001 can be readily conveyed in a liquid state. For example, the aluminum compound can be supplied in a liquid state to a precursor cartridge. The precursor supply unit 20 can be configured to house the precursor cartridge therein. In another embodiment, the aluminum compound can be dissolved in an organic solvent to prepare a precursor solution. If the deposition precursor is supplied in the form of a precursor solution, the deposition precursor can be from about 0.01 mol / L to about 2.0 mol / L, or from about 0.05 mol / L to about 1.0 mol / L, relative to the organic solvent. The precursor solution can be supplied to the precursor cartridge. The precursor cartridge can then be placed in the precursor supply unit 20. The precursor supply unit 20 can supply the deposition precursor into the interior space of the chamber 10.

[0087] Organic solvents may include acetate solvents, ether solvents, ketone solvents, hydrocarbon solvents, and / or heterocyclic aromatic solvents. The water concentration in the organic solvent may be less than about 10 ppm or less than about 1 ppm. Acetate solvents may include ethyl acetate, butyl acetate, and / or methoxyethyl acetate. Ether solvents may include tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether, and / or diethyl ether. Alkane. Ketone solvents may include methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl pentyl ketone, cyclohexanone and / or methyl cyclohexanone.

[0088] Hydrocarbon solvents can include both unsaturated and saturated hydrocarbon solvents. Hydrocarbon solvents can include hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, toluene, and / or xylene. Hydrocarbon solvents can be hydrocarbon solvents containing a cyano group. In this case, hydrocarbon solvents containing a cyano group can include 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, benzonitrile, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane, and / or 1,4-dicyanobenzene. Heteroaromatic solvents can include pyridine and / or dimethylpyridine.

[0089] In addition to the aluminum compound, the deposition precursor 2001 may also contain other precursors. These other precursors may be supplied to chamber 10 via a supply path, and may be supplied to chamber 10 separately from the aluminum compound. In another embodiment, the aluminum compound and the other precursors may be mixed to prepare a mixed precursor. The mixed precursor may be supplied to chamber 10. The other precursors may include at least one selected from the group consisting of semiconductor compounds, metal compounds, and organic compounds. However, embodiments of the inventive concept are not limited thereto. The concentration of water in the other precursors may be less than about 10 ppm or less than about 1 ppm.

[0090] Semiconductor compounds may include silicon and / or germanium.

[0091] Metal compounds may include magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, manganese, iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, gallium, indium, germanium, tin, lead, antimony, bismuth, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, and / or ytterbium.

[0092] The organic compound may include at least one selected from the group consisting of alcohols, diols, β-diketones, cyclopentadienes, and amines. The organic compound may provide an organic ligand, and the deposited film may contain the organic ligand.

[0093] Alcohol compounds may include, for example, alkyl alcohol compounds or ether alcohol compounds. Alkyl alcohol compounds may refer to alcohol compounds having an alkyl group. For example, alkyl alcohol compounds may include methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, isobutanol, tert-butanol, pentanol, isoamyl alcohol, and / or tert-amyl alcohol.

[0094] Ether alcohols can refer to alcohols containing an ether group. For example, ether alcohols 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.

[0095] Diol compounds may include, for example, 1,2-ethylene glycol, 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.

[0096] β-Diketone compounds may include alkyl-substituted β-diketone compounds, fluorine-substituted β-diketone compounds, and / or ester-substituted β-diketone compounds. Alkyl-substituted β-diketone compounds may include acetylacetone, hexane-2,4-diketone, 5-methylhexane-2,4-diketone, heptane-2,4-diketone, 2-methylheptane-3,5-diketone, 5-methylheptane-2,4-diketone, 6-methylheptane-2,4-diketone, 2,2-dimethylheptane-3,5-diketone, 2,6-dimethylheptane-3,5-diketone, 2,2,6-trimethylheptane-3,5-diketone, etc. Methylheptane-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 / or 2,2-dimethyl-6-ethyldecane-3,5-dione. Fluorine-substituted β-diketone compounds may 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. Ester-substituted β-diketone compounds may include 1,1,5,5-tetramethyl-1-methoxyhexane-2,4-diketone, 2,2,6,6-tetramethyl-1-methoxyheptane-3,5-diketone and / or 2,2,6,6-tetramethyl-1-(2-methoxyethoxy)heptane-3,5-diketone.

[0097] Cyclopentadiene compounds may include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, sec-butylcyclopentadiene, isobutylcyclopentadiene, tert-butylcyclopentadiene, dimethylcyclopentadiene, and / or tetramethylcyclopentadiene.

[0098] Amine compounds may include methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, ethylmethylamine, propylmethylamine and / or isopropylmethylamine.

[0099] like Figure 1 , Figure 2 and Figure 3A As described above, a deposition precursor 2001 can be supplied into chamber 10 to form a precursor layer 2100 on substrate 1000 (S20). The deposition precursor 2001 may comprise the aluminum compound described above. The deposition precursor 2001 can be adsorbed onto the top surface 1000a of substrate 1000 to form the precursor layer 2100. During the supply of deposition precursor 2001 to chamber 10, the temperature of substrate 1000 can be maintained at approximately 25°C to approximately 400°C, or approximately 200°C to approximately 300°C. During the supply of deposition precursor 2001 to chamber 10, the pressure in chamber 10 can be approximately 10 Pa to approximately 1,013 hPa.

[0100] The deposition precursor 2001 can be supplied to chamber 10 via a gas delivery method. The liquid deposition precursor 2001 can be heated, and the pressure can be reduced in the precursor supply unit 20, thereby causing the deposition precursor 2001 to evaporate. In another embodiment, the deposition precursor 2001 can be supplied to chamber 10 via a liquid delivery method. In this case, a separate evaporation chamber (not shown) can be provided between the precursor supply unit 20 and chamber 10. The deposition precursor 2001 can be supplied to the evaporation chamber in a liquid state. The deposition precursor 2001 can be heated, and the pressure can be reduced in the evaporation chamber, thereby causing the deposition precursor 2001 to evaporate. Thus, a gaseous deposition precursor 2001 can be formed. The gaseous deposition precursor 2001 can be supplied to chamber 10 alone, or it can be supplied to chamber 10 together with a carrier gas. The carrier gas can include inert gases such as argon, nitrogen, and helium.

[0101] After the precursor layer 2100 is formed, a first venting process (S21) can be performed. During the first venting process, the remaining deposited precursor 2001 and byproduct gases can be removed from chamber 10. The first venting process can include a purging process, a pressure reduction process, or a combination thereof. For example, the purging process can be performed by supplying an inert gas into chamber 10. The inert gas can include argon, nitrogen, and / or helium. The pressure reduction process can include reducing the pressure in chamber 10. The pressure reduction process can be performed until the pressure in chamber 10 becomes about 0.01 Pa to about 300 Pa, or about 0.01 Pa to about 100 Pa.

[0102] like Figure 1 , Figure 2 and Figure 3B As described above, the reactant gas can be supplied to chamber 10 and a thin film can be formed (S30). The reactant gas can react with precursor layer 2100. For example, the reactant gas can react with deposition precursor 2001 adsorbed on substrate 1000. Therefore, a thin film 2000 can be formed on substrate 1000. The reactant gas can include at least one selected from the group consisting of oxidizing gases, reducing gases, and nitrogen-containing gases. Oxidizing gases can include, for example, oxygen, ozone, nitrogen dioxide, nitric oxide, water vapor, hydrogen peroxide, acetic acid, and / or acetic anhydride. Reducing gases can include hydrogen. Nitrogen-containing gases can include organic amine compounds, hydrazine compounds, and / or ammonia. Organic amine compounds can include mono(alkyl)amines, dialkylamines, trialkylamines, and / or alkylene diamines. In another embodiment, the reactant gas can include NO2, N2O (nitrous oxide), CO2, H2O2, HCOOH, CH3COOH, and / or (CH3CO)2O. When using a nitrogen-containing gas as the reactant gas, the deposited thin film 2000 may include an aluminum nitride layer or an aluminum-containing composite nitride layer. When using an oxidizing gas as the reactant gas, the deposited thin film 2000 may contain oxygen. For example, the deposited thin film 2000 may include an aluminum oxide layer or an aluminum-containing composite oxide layer. During the supply of reactant gas to chamber 10, the temperature of substrate 1000 may be maintained at approximately 25°C to approximately 400°C, or approximately 200°C to approximately 300°C. During the supply of reactant gas to chamber 10, the pressure of the chamber may be approximately 10 Pa to approximately 1,013 hPa.

[0103] According to an exemplary embodiment, the temperature of the deposition process can be from about 300°C to about 600°C. The temperature of the deposition process can refer to the temperature in chamber 10. The temperature of the deposition process can include at least one of the temperature of chamber 10 during the supply of the deposition precursor (S20) or the temperature of chamber 10 during the supply of the reactive gas (S30).

[0104] During the step of supplying the reaction gas, the pressure in chamber 10 can be from about 10 Pa to about 1,013 hPa.

[0105] During the deposition process (S30), energy may be additionally supplied to chamber 10. The energy may include at least one of plasma, light, heat, or voltage. For example, the deposition process can be performed by atomic layer vapor deposition. Energy can be supplied during at least one of the following processes: supplying precursor gas (S20), performing a first exhaust process (S21), supplying reactant gas (S30), or performing a second exhaust process (S31). The deposition process can be performed by thermal CVD, plasma CVD, photoCVD, or photoplasmochemical CVD.

[0106] According to an exemplary embodiment, the material of the thin film 2000 can be determined based on the type of aluminum compound, the type of reactant gas, and the type of additional deposition precursor 2001 during the deposition process. The thin film 2000 may include an aluminum-containing layer. The aluminum-containing layer may include a metal, oxide ceramic, and / or nitride ceramic. The aluminum-containing layer may include, for example, an aluminum layer, an aluminum nitride layer, an alumina layer, and / or an aluminum composite oxide layer. The aluminum composite oxide layer may include an aluminum oxynitride layer, an aluminum metal oxide layer, and / or an aluminum oxycarbide layer. The aluminum composite oxide layer may contain aluminum and a metal different from aluminum. In another embodiment, the aluminum composite oxide layer may include AlSi. x O y ZrAl x SiO y TiAl x Si x O y and / or HfAl x SiO y (where x and y are real numbers). For example, aluminum composite oxide layers may include AlSi. 0.8-1.2 O 3.1-3.9 ZrAl2SiO7, TiAl2SiO7 and / or HfAl2SiO7.

[0107] The deposition rate of thin film 2000 can be controlled by the supply conditions of deposition precursor 2001, the temperature of substrate 1000, and the pressure of chamber 10. The supply conditions of deposition precursor 2001 may include the evaporation temperature of deposition precursor 2001 and the pressure of the evaporated deposition precursor 2001. The thickness of thin film 2000 deposited in each cycle can be determined by the deposition rate. In the case of a deposition process performed by atomic layer deposition, the deposition rate can be evaluated by the thickness of thin film 2000 deposited in each cycle. In the following explanation, unless otherwise stated, the thickness of thin film 2000 may refer to the thickness of thin film 2000 deposited in each cycle. A cycle may refer to a process used to form a single thin film 2000. For example, Figure 1The supply of deposition precursor 2001 (S20), the first exhaust process (S21), the supply of reaction gas (S30), and the second exhaust process (S31) can constitute a cycle.

[0108] If the deposition rate is too slow (e.g., less than about 0.01 nm / min), the productivity of the thin film 2000 may decrease. If the deposition rate is too fast (e.g., greater than about 100 nm / min), the thin film 2000 may be deposited as a large thickness. Additionally, the properties of the thin film 2000 may be degraded. According to an exemplary embodiment, the aluminum compound has thermal stability, and the deposition rate can be from about 0.05 nm / min to about 100 nm / min, or from about 1 nm / min to about 50 nm / min. Therefore, the thin film 2000 can have a small thickness and can exhibit improved properties. For example, the deposition thickness of the thin film 2000 per cycle can be about [missing information - likely a number]. to approximately According to an exemplary embodiment, the thickness of the thin film 2000 can be reduced, and the semiconductor device can be miniaturized and have a reduced pitch.

[0109] According to an exemplary embodiment, the groups in Formula 1 that include Z bonded to Al can be relatively (volume-wise) large. Therefore, when using an aluminum compound represented by Formula 1, the film 2000 can be deposited to even smaller thicknesses.

[0110] After forming the thin film 2000, an annealing process can be performed on it. The annealing process can be carried out in an inert gas atmosphere, an oxidizing gas atmosphere, or a reducing gas atmosphere. The annealing process can improve the electrical properties of the thin film 2000. In this case, the electrical properties may include insulating properties. The annealing process can also make the thin film 2000 more dense.

[0111] After the film 2000 is formed, a reflow process can be performed on the film 2000. The reflow process can improve the step coverage of the film 2000. The reflow process can be carried out at temperatures from about 250°C to 1,000°C or from about 300°C to about 500°C.

[0112] After the thin film 2000 is formed, a second venting process (S31) can be performed. During the second venting process, the remaining reaction gases and byproduct gases after the reaction can be removed from chamber 10. The second venting process may include a purging process, a pressure reduction process, or a combination thereof, as described above.

[0113] According to an exemplary embodiment, after the supply of the deposition precursor 2001 (S20) is performed, the supply of the reaction gas (S30) can be performed. In another embodiment, the supply of the reaction gas (S30) and the supply of the deposition precursor 2001 (S20) can be performed simultaneously. In this case, the first venting process (S21) can be omitted.

[0114] The thin film 2000 formation process described above can be performed multiple times on the substrate 1000. For example, the thin film 2000 formation process can be repeated in cycles. In this case, the thin film 2000 may include multiple stacked thin films 2000. Therefore, the total thickness of the thin film 2000 can be controlled.

[0115] According to exemplary embodiments, the thin film 2000 can be used as wiring for integrated circuits, hard coatings for components, gate insulating layers for transistors, insulating layers for storage devices, dielectric layers for capacitors, magnetoresistive heads for hard disks, optical glass for optical communication circuits, and / or catalysts. However, embodiments of the present invention are not limited thereto.

[0116] Figures 4A to 4J This is a diagram illustrating a method for manufacturing a semiconductor device according to an exemplary embodiment.

[0117] Reference Figure 4A A substrate 1000A comprising multiple active regions AC is fabricated. The substrate 1000A may be a semiconductor substrate. The active regions AC are defined by device isolation regions 112. Device isolation regions 112 may be disposed between the active regions AC. Device isolation regions 112 may contain a silicon-based insulating material. The silicon-based insulating material may include silicon oxide, silicon nitride, silicon oxynitride, or combinations thereof.

[0118] An insulating interlayer 120 may be formed on the substrate 1000A. The insulating interlayer 120 may include a silicon oxide layer. Conductive components 124 may be formed in the insulating interlayer 120 and connected to the active region AC. The conductive components 124 may extend through the insulating interlayer 120. The plurality of conductive components 124 may comprise polysilicon, metal, conductive metal nitride, metal silicide, or a combination thereof.

[0119] Reference Figure 4B An insulating layer 128 can be formed on the insulating interlayer 120 and the conductive component 124. The insulating layer 128 can serve as an etching stop layer. A mold layer (which will be formed in subsequent processes) can be used relative to the insulating interlayer 120 and the conductive component 124. Figure 4C The insulating layer 128 is formed by using an etch-selective insulating material (130) as described above. The insulating layer 128 may contain, for example, a silicon-based insulating material.

[0120] Reference Figure 4CA molding layer 130 may be formed on the insulating layer 128. The molding layer 130 may include an oxide layer.

[0121] Reference Figure 4D A sacrificial pattern 142 and a mask pattern 144 can be sequentially formed on the mold layer 130. The sacrificial pattern 142 may include an oxide layer. The sacrificial pattern 142 can protect the upper part of the mold layer 130. The mask pattern 144 may include an oxide layer, a nitride layer, a polysilicon layer, a photoresist layer, or a combination thereof.

[0122] Reference Figure 4E The mask pattern 144 can be used as an etching mask to etch the sacrificial pattern 142 and the mold layer 130. The etching can be dry etching. Through the etching process, a plurality of holes H1 can be formed in the sacrificial pattern 142 and the mold layer 130. The holes H1 can be spaced apart from each other and can extend through the sacrificial pattern 142 and the mold layer 130. In this case, the insulating layer 128 can be further etched, and the holes H1 can extend into the insulating layer 128. The holes H1 can expose the conductive component 124. Afterwards, the mask pattern 144 can be removed to expose the top surface of the sacrificial pattern 142.

[0123] Reference Figure 4F A conductive layer 150 can be formed in the hole H1 and on the sacrificial pattern 142. The conductive layer 150 can conformally cover the top surface of the conductive component 124 exposed by the hole H1, the inner sidewall of the insulating layer 128, the inner sidewall of the mold layer 130, and the inner sidewall and top surface of the sacrificial pattern 142.

[0124] The conductive layer 150 can be formed using, for example, doped semiconductors, conductive metal nitrides, metals, metal silicides, conductive oxides, or combinations thereof. 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 combinations thereof can be used to form the conductive layer 150. The conductive layer 150 can be formed by deposition methods. For example, the conductive layer 150 can be formed by chemical vapor deposition (CVD), metal-organic chemical vapor deposition (MOCVD), or atomic layer deposition (ALD).

[0125] Reference Figure 4GThe upper part of the conductive layer 150 can be removed, and multiple lower electrodes LE can be formed. The conductive layer 150 can be removed by an etching process or a chemical mechanical polishing (CMP) process. The sacrificial pattern 142 can be removed simultaneously with the removal of the conductive layer 150. The conductive layer 150 can be removed until the top surface of the molding layer 130 is exposed. Each lower electrode LE can have a cylindrical shape. Contrary to the accompanying drawings, the lower electrode LE can be a cylindrical lower electrode without internal space.

[0126] Reference Figure 4H The template layer 130 can be removed, exposing the outer wall of the lower electrode LE and the top surface of the insulating layer 128. The template layer 130 can be removed by an etching process. The etching process may include a wet etching process.

[0127] Reference Figure 4I A dielectric layer 2000A can be formed to cover the lower electrode LE. The dielectric layer 2000A can conformally cover the exposed surface of the lower electrode LE. The exposed surface can include the inner sidewall, outer sidewall, and top surface of the lower electrode. The dielectric layer 2000A can also cover the top surface of the insulating layer 128.

[0128] You can refer to Figure 1 , Figure 2 , Figure 3A and Figure 3B The described thin film formation method forms the dielectric layer 2000A. For example, the dielectric layer 2000A can be formed by a deposition process using a deposition precursor comprising an aluminum compound. The deposition process can be an atomic layer deposition (ALD) process. The aluminum compound according to the exemplary embodiment can have thermal stability, and the dielectric layer 2000A can be formed to a small thickness. For example, the dielectric layer 2000A can be a single thin film and can have approximately to approximately The thickness. In another embodiment, the dielectric layer 2000A may comprise a plurality of thin films, and each thin film may have approximately to approximately The thickness of the dielectric layer. The 2000A dielectric layer can exhibit excellent properties. These properties may include insulating properties.

[0129] The dielectric layer 2000A may include an aluminum-containing layer. In one embodiment, the dielectric layer 2000A may include an aluminum oxide layer and a high-k dielectric layer. In this case, it can be referred to... Figure 1 , Figure 2 , Figure 3A and Figure 3BThe described thin film formation method forms an alumina layer. The high-k dielectric layer may include a hafnium oxide layer, a tantalum oxide layer, and / or a zirconium oxide layer. The high-k dielectric layer can have a crystalline structure. As the thickness of the alumina layer decreases, the high-k dielectric layer can have even more improved crystalline structures. Therefore, the dielectric properties of the dielectric layer can be improved by 2000 Å.

[0130] The lower electrode LE can have a large aspect ratio (height-to-diameter ratio) and can increase the capacitance of the capacitor (170 in Figure 4). According to an exemplary embodiment, the deposition process using an aluminum compound as a deposition precursor can exhibit excellent step coverage properties. Therefore, the lower electrode LE can be smoothly sealed with a dielectric layer 2000A. The deposition process can be performed at about 300°C to about 600°C. The formation of the dielectric layer 2000A can also include annealing at about 500°C to about 1,150°C.

[0131] Reference Figure 4J An upper electrode UE can be formed on the dielectric layer 2000A. The upper electrode UE can contain conductive materials, such as doped semiconductors, conductive metal nitrides, metals, metal silicides, and conductive oxides. The upper electrode UE can be formed by chemical vapor deposition (CVD), metal-organic chemical vapor deposition (MOCVD), or atomic layer deposition (ALD). Using the lower electrode LE, the dielectric layer 2000A, and the upper electrode UE, a capacitor 170 can be formed.

[0132] The semiconductor device 100 can be manufactured using the formation methods described so far. The semiconductor device 100 may include a capacitor 170. The manufacturing process of the semiconductor device 100 may include depositing a dielectric layer 2000A.

[0133] Figures 5A to 5I This is a diagram illustrating a method for manufacturing a semiconductor device according to an exemplary embodiment.

[0134] Reference Figure 5A An etch stop layer 222, a sacrificial layer 224, and an insulating layer 226 can be formed on the substrate 1000B. The substrate 1000B may contain semiconductor elements such as Si and Ge. In another embodiment, the substrate 1000B may contain compound semiconductors such as SiC, GaAs, InAs, and InP.

[0135] An etch stop layer 222 may be formed on the top surface of the substrate 1000B. The etch stop layer 222 may contain, for example, silicon oxide.

[0136] Multiple sacrificial layers 224 and multiple insulating layers 226 can be alternately and repeatedly stacked on the etch stop layer 222. The thickness of the uppermost insulating layer 226 can be greater than the thickness of the other insulating layers 226. The insulating layer 226 may comprise, for example, silicon oxide. The sacrificial layer 224 may have a different etch selectivity than the etch stop layer 222 and the insulating layer 226. The sacrificial layer 224 may comprise, for example, a silicon nitride layer, a silicon oxynitride layer, a polysilicon layer, or a polysilicon germanium layer.

[0137] Reference Figure 5B A via 230 can be formed to pass through the insulating layer 226, the sacrificial layer 224, and the etch stop layer 222. The via 230 can expose the substrate 1000B.

[0138] Reference Figure 5C A charge storage pattern 232, a tunnel insulating pattern 234, a semiconductor pattern 240, and an embedded insulating layer 242 can be formed in each channel hole 230. The charge storage pattern 232 can cover the inner wall of the channel hole 230. The charge storage pattern 232 may include, for example, a silicon nitride layer. A tunnel insulating pattern 234 can be formed on the sidewall of the charge storage pattern 232 in each channel hole 230. The tunnel insulating pattern 234 may include, for example, a silicon oxide layer. A semiconductor pattern 240 can be formed in each channel hole 230 to cover the sidewall of the tunnel insulating pattern 234 and the top surface of the substrate 1000B. The semiconductor pattern 240 can function as a channel region. An embedded insulating layer 242 can be formed on the semiconductor pattern 240 to fill each channel hole 230. The embedded insulating layer 242 can be formed using, for example, a high-density plasma oxide layer, a spin-coated glass (SOG) layer, and / or a CVD oxide layer. The charge storage pattern 232, the tunnel insulation pattern 234, the semiconductor pattern 240, and the embedded insulation layer 242 can be positioned in each channel hole 230.

[0139] Conductive pads 250 can be formed on top of the channel hole 230. Each conductive pad 250 can be formed on the charge storage pattern 232, the tunnel insulating pattern 234, the semiconductor pattern 240, and the embedded insulating layer 242. The conductive pads 250 can be formed using impurity-doped semiconductor materials or conductive materials such as metals. The bottom surface of the conductive pads 250 can be arranged at a level higher than the upper surface of the uppermost sacrificial layer 224. The conductive pads 250 can function as drain areas.

[0140] Although not shown, a capping layer may also be formed on the uppermost insulating layer 226 and the conductive pad 250. The capping layer may contain insulating material.

[0141] Reference Figure 5DAn opening 260 can be formed to pass through the insulating layer 226, the sacrificial layer 224, and the etch stop layer 222. The opening 260 can expose the substrate 1000B. Each of the openings 260 can be a word line cut area.

[0142] Reference Figure 5E The sacrificial layer 224 exposed by the opening 260 can be removed to form the gate region GS. The sacrificial layer 224 can be removed via an etching process. The gate region GS can be disposed between the etch stop layer 222 and the bottommost insulating layer 226, and between the insulating layers 226. The gate region GS can be an empty space. The gate region GS can be connected to at least one of the openings 260. The gate region GS can expose the charge storage pattern 232.

[0143] Reference Figure 5F A barrier insulating layer 2000B can be formed to cover the inner wall of the gate region GS. The barrier insulating layer 2000B may include an aluminum-containing layer.

[0144] You can refer to the above. Figure 1 , Figure 2 , Figure 3A and Figure 3B The described thin film formation method forms the barrier insulating layer 2000B. For example, the barrier insulating layer 2000B can be formed by a deposition process using a deposition precursor containing an aluminum compound. The deposition process can be an atomic layer deposition (ALD) process. The deposition precursor can be supplied via opening 260. The aluminum compound according to the exemplary embodiment can have thermal stability, and the barrier insulating layer 2000B can be formed to have a thin thickness. For example, the barrier insulating layer 2000B can be a single thin film and can have approximately to approximately The thickness. In another embodiment, the barrier insulating layer 2000B may comprise a plurality of thin films, and each film may have approximately to approximately The thickness of the barrier insulation layer 2000B is significant. It exhibits excellent properties.

[0145] The deposition process can be carried out at approximately 300°C to approximately 600°C. The formation of the barrier insulating layer 2000B may also include annealing at approximately 500°C to approximately 1,150°C. The annealing process can densify the barrier insulating layer 2000B.

[0146] Reference Figure 5GA gate conductive layer 264P can be formed on the barrier insulating layer 2000B. The gate conductive layer 264P can fill the gate region GS. The gate conductive layer 264P may include a first conductive barrier layer and a first conductive layer. The first conductive barrier layer may contain a conductive metal nitride, such as TiN or TaN. The first conductive barrier layer may be in physical contact with the barrier insulating layer 2000B. The first conductive layer may contain conductive polysilicon, a metal, a metal silicide, or a combination thereof.

[0147] Reference Figure 5H The gate conductive layer 264P and the barrier insulating layer 2000B can be patterned to form the gate 264 and the barrier insulating pattern 2000B', respectively. The gate conductive layer 264P and the barrier insulating layer 2000B can be patterned through an etching process. The gate conductive layer 264P and the barrier insulating layer 2000B can be patterned through a single process. The gate conductive layer 264P and the barrier insulating layer 2000B can be etched until the sidewalls of the insulating layer 226 and the upper surface of the substrate 1000B are exposed. Therefore, the gate 264 and the barrier insulating pattern 2000B' can be formed.

[0148] The aluminum compound according to the exemplary embodiment may be free of impurities or may contain very low concentrations of impurities. Therefore, the barrier insulating pattern 2000B' may include an alumina layer that is free of impurities or contains very low concentrations of impurities. Impurities may be, for example, carbon residues.

[0149] For reference Figure 5F As can be seen, since the annealing process can densify the barrier insulating layer 2000B, over-etching of the barrier insulating layer 2000B can be prevented during the etching of the barrier insulating layer 2000B and the gate conductive layer 264P.

[0150] After forming the gate 264 and the barrier insulating pattern 2000B', impurities can be implanted onto the exposed substrate 1000B. In this way, a common source region 268 can be formed in the substrate 1000B.

[0151] Reference Figure 5I Insulating spacers 272 can be formed in the opening 260. The insulating spacers 272 can cover the inner sidewall of the opening 260. The insulating spacers 272 can expose the common source region 268. The insulating spacers 272 can contain a silicon-based insulating material.

[0152] Conductive plugs 274 can be formed in the openings 260. Conductive plugs 274 can be formed on the sidewalls of the insulating spacers 272 to fill the openings 260. The conductive plugs 274 can be connected to the common source regions 268. The conductive plugs 274 may include a second conductive barrier layer and a second conductive layer. The second conductive barrier layer can be in physical contact with the respective insulating spacers 272. The second conductive barrier layer may contain a conductive metal nitride, such as TiN or TaN. The second conductive layer can be disposed on the second conductive barrier layer and can fill the openings 260. A metal such as tungsten can be used to form the second conductive layer.

[0153] A first contact 282 can be formed on the conductive plug 274. A first conductive layer 284 can be formed on the first contact 282. A metal, a metal nitride, or a combination thereof can be used to form the first contact 282 and the first conductive layer 284.

[0154] Second contacts 292 can be formed on and connected to conductive pads 250 respectively. Bit lines 294 can be formed in the second contacts 292 to connect to them. Metals, metal nitrides, or combinations thereof can be used to form the second contacts 292 and the bit lines 294. A semiconductor device 200 can be manufactured using the forming method described so far. The semiconductor device 200 can be a non-volatile memory device.

[0155] Figures 6A to 6D This is a diagram illustrating a method for manufacturing a semiconductor device according to an exemplary embodiment.

[0156] Reference Figure 6A A conductive pattern 312 can be formed on the substrate 1000C. The conductive pattern 312 can be a source / drain region, a gate, or a wiring layer. The conductive pattern 312 can contain metal or doped semiconductor material.

[0157] An insulating interlayer pattern 314 can be formed on a substrate 1000C. The insulating interlayer pattern 314 may have vias 314H. The vias 314H may expose at least a portion of the conductive pattern 314. The insulating interlayer pattern 314 may contain a silicon-based insulating material.

[0158] Reference Figure 6B A conductive barrier layer 2000C can be formed in the hole 314H. The conductive barrier layer 2000C can conformally cover the top surface of the conductive pattern 312 exposed by the hole 314H, as well as the top surface and inner sidewalls of the interlayer insulating pattern 314. The conductive barrier layer 2000C may include an aluminum nitride layer.

[0159] You can refer to the above. Figure 1 , Figure 2 , Figure 3A and Figure 3B The described thin film formation method forms a conductive barrier layer 2000C. The conductive barrier layer 2000C can be formed by using a deposition process of an aluminum compound according to an exemplary embodiment. The deposition process can be an atomic layer deposition (ALD) process. The aluminum compound can have thermal stability, and the conductive barrier layer 2000C can be formed to a thin thickness. For example, the conductive barrier layer 2000C can be a single thin film and can have approximately [missing information - likely a thickness]. to approximately The thickness. In another embodiment, the conductive barrier layer 2000C may comprise a plurality of thin films, and each thin film may have approximately to approximately The thickness of the conductive barrier layer 2000C is significant. This allows it to exhibit excellent properties.

[0160] Reference Figure 6C A wiring layer 330 can be formed on the conductive barrier layer 2000C to fill the via 314H. The top surface of the wiring layer 330 can be located at a level higher than the top surface of the interlayer pattern 314. A metal such as tungsten or copper can be used to form the wiring layer 330.

[0161] Reference Figure 6D The wiring layer 330 can be planarized, and a wiring pattern 331 can be formed. Planarization of the wiring layer 330 can be performed through an etch-back process or a chemical mechanical polishing process. During the planarization process of the wiring layer 330, a portion of the conductive barrier layer 2000C can be removed to form a conductive barrier pattern 2000C'. A portion of the conductive barrier layer 2000C can be a portion disposed on the top surface of the interlayer insulating pattern 314. The wiring layer 330 can be planarized until the top surface of the interlayer insulating pattern 314 is exposed. The wiring pattern 331 and the conductive barrier pattern 2000C' can be positioned in the via 314H. Therefore, the fabrication of the semiconductor device 300 can be completed. Because the conductive barrier pattern 2000C' has a thin thickness, the semiconductor device 300 can be highly integrated and miniaturized.

[0162] Figure 7A This is a plan view illustrating a semiconductor device according to an exemplary embodiment. Figure 7B It is shown Figure 7A A three-dimensional view of a semiconductor device. Figure 7C This is a diagram illustrating a method for manufacturing a semiconductor device according to an exemplary embodiment, and it is along... Figure 7A Cross-sectional views obtained from lines I-I' and II-II' in the diagram.

[0163] Reference Figures 7A to 7CThe semiconductor device 400 may include a substrate 1000D, a device isolation layer 410, and a gate structure 420. The semiconductor device 400 may be a transistor. The substrate 1000D may have protruding fin-like members F. The fin-like members F may extend along a first direction D1. The first direction D1 may be parallel to the bottom surface of the substrate 1000D. The device isolation layer 410 may be formed on the substrate 1000D to cover the lower sidewalls of the fin-like members F. The device isolation layer 410 may include a silicon oxide layer, a silicon nitride layer, a silicon oxynitride layer, or a combination thereof. The device isolation layer 410 may expose the upper portion of the fin-like members F.

[0164] A gate structure 420 can be formed on the substrate 1000D to cross the fin-shaped member F. The gate structure 420 can extend along a second direction D2. The second direction D2 can be parallel to the bottom surface of the substrate 1000D and intersect with the first direction D1.

[0165] Source / drain regions 430 can be formed on both sides of the fin-shaped component F. The source / drain regions 430 can be formed by selective epitaxial growth using the fin-shaped component F as a seed crystal. The source / drain regions 430 can contain silicon, silicon-germanium, and / or silicon carbide. The shapes of the source / drain regions 430 can be varied.

[0166] like Figure 7C As shown, the gate structure 420 may include a stacked interface layer 412, a high-k dielectric layer 414, and a gate pattern 420G. The interface layer 412 may be disposed on the upper surface of the fin member F. The interface layer 412 may include a silicon-based insulating material, such as an oxide layer, a nitride layer, or an oxynitride layer. The high-k dielectric layer 414 may have a dielectric constant greater than that of the silicon oxide layer. For example, the high-k dielectric layer 414 may have a dielectric constant of about 10 to about 25. The high-k dielectric layer 414 may comprise a metal oxide or a metal oxynitride.

[0167] The gate pattern 420G may include a first metal-containing layer 426, a second metal-containing layer 2000D, and a void-filling metal layer 428. The first metal-containing layer 426 may contain a P-type work function conductive material, such as TiN. The second metal-containing layer 2000D may contain an N-type work function conductive material, such as an aluminum compound containing Ti or Ta. In another embodiment, the second metal-containing layer 2000D may contain an aluminum compound containing carbon atoms. In this case, the second metal-containing layer 2000D may contain TiAlC, TiAlCN, TaAlC, TaAlCN, or a combination thereof. In another embodiment, the second metal-containing layer 2000D may contain TiAl, TiAlN, TaAlN, or a combination thereof. The first metal-containing layer 426 and the second metal-containing layer 2000D can control the work function of the gate structure 420. Therefore, the threshold voltage of the gate structure 420 can be controlled.

[0168] You can refer to the above. Figure 1 , Figure 2 , Figure 3A and Figure 3B The described thin film formation method forms the second metal-containing layer 2000D. For example, the second metal-containing layer 2000D can be formed by a deposition process using a deposition precursor containing an aluminum compound. The deposition process can be an atomic layer deposition (ALD) process. The aluminum compound layer can have thermal stability, and the second metal-containing layer 2000D can be formed to have a small thickness. For example, the second metal-containing layer 2000D can be a single thin film and can have approximately [missing information - likely a thickness]. to approximately The thickness. In another embodiment, the second metal-containing layer 2000D may comprise a plurality of thin films, and each thin film may have approximately to approximately The thickness. The second metal layer 2000D exhibits excellent properties.

[0169] A void-filling metal layer 428 may be disposed on the second metal-containing layer 2000D. The void-filling metal layer 428 may comprise aluminum, tungsten, metal nitrides (e.g., TiN and TaN), metal carbides, metal silicides, aluminum carbide, aluminum nitride, and / or silicon nitride. The gate structure 420 may be formed by an alternative metal gate (RMG) process.

[0170] Dielectric spacers 442 can be disposed on both sides of the gate structure 420. A dielectric interlayer 444 can be formed on the source / drain region 430. The dielectric interlayer 444 can cover the sidewalls of the dielectric spacers 442. The dielectric interlayer 444 can contain a silicon-based insulating material.

[0171] The semiconductor device 400 can be manufactured using the manufacturing implementation scheme described so far. The semiconductor device 400 can be a transistor. The second metal layer 2000D can have a small thickness, and the semiconductor device 400 can be highly integrated and miniaturized.

[0172] In the following sections, aluminum compounds and methods for forming thin films using said aluminum compounds will be described with reference to experimental and comparative examples.

[0173] In the experimental and comparative examples, elemental analysis can be performed using inductively coupled plasma atomic emission spectrometry (ICP-AES).

[0174] In the experimental and comparative examples, nuclear magnetic resonance (NMR) analysis was performed using deuterated benzene solvent. The NMR analysis results are displayed as (chemical shift: multiplicity: number of H atoms).

[0175] Thermal analysis was performed in the experimental and comparative examples using a thermogravimetric-differential thermal analysis (TG-DTA) apparatus. Argon gas was supplied at a rate of 100 ml / min. The temperature rise rate was approximately 10 °C / min. The temperature was measured at the point where the weight of the sample initially supplied to the apparatus became 50% by weight (hereinafter, the 50% weight reduction temperature).

[0176] <Example 1> Preparation of aluminum compound No. 2

[0177] Trimethylaluminum was dissolved in toluene to prepare a trimethylaluminum / toluene solution. 8.09 mL (14.6 mmol) of the trimethylaluminum / toluene solution and 10 mL of anhydrous toluene were added to a 50 mL three-necked flask. The trimethylaluminum / toluene solution was then cooled to approximately 0 °C, and 2.25 g (14.6 mmol) of N,N'-diethyl-2,4-pentanediimide was added to prepare a mixed solution. The mixed solution was stirred at approximately 0 °C for approximately 3 hours, and the solvent was distilled from the mixed solution to give 2.20 g (72% yield) of the product.

[0178] [Elemental Analysis]

[0179] Al: 12.5% ​​by weight (calculated value 12.8%)

[0180] C: 63.1 wt%, H: 11.5 wt%, N: 12.8 wt% (calculated; C: 62.8%, H: 11.0%, N: 13.3%)

[0181] Nuclear magnetic resonance (NMR) 1 [H-NMR analysis]

[0182] (4.40:s:1H)(3.04:q:4H)(1.53:s:6H)(0.95:t:6H)(-0.29:s:6H)

[0183] [Thermal Analysis]

[0184] Using a sample of 9,614 mg, the 50% wt% temperature reduction was measured to be approximately 174 °C.

[0185] <Example 2> Preparation of aluminum compound No. 3

[0186] 33.1 mL (59.6 mmol) of trimethylaluminum / toluene solution and 25 mL of anhydrous toluene were added to a 200 mL four-necked flask. The trimethylaluminum / toluene solution was then cooled to approximately 0 °C, and 10.9 g (59.6 mmol) of N,N'-diisopropyl-2,4-pentanediimide was added to prepare a mixture solution. The mixture solution was stirred at room temperature (25 °C) for approximately 5 hours. The solvent was distilled from the mixture solution to give 12.0 g (84% yield) of the product.

[0187] [Elemental Analysis]

[0188] Al: 11.7% by weight (calculated value 11.3%)

[0189] C: 65.2 wt%, H: 11.7 wt%, N: 11.4 wt% (calculated; C: 65.5%, H: 11.4%, N: 11.8%)

[0190] Nuclear magnetic resonance (NMR) 1 [H-NMR analysis]

[0191] (4.41:s:1H)(3.54:sep:2H)(1.60:s:6H)(1.20:d:12H)(-0.18:s:6H)

[0192] [Thermal Analysis]

[0193] Using a sample of 10,197 mg, the 50% wt% reduction in temperature was measured to be approximately 188 °C.

[0194] <Example 3> Preparation of Aluminum Compound No. 5

[0195] Add 81 ml (146 mmol) of trimethylaluminum / toluene solution and 80 ml of anhydrous toluene to a 300 ml four-necked flask. Then, stir the solution and cool to approximately 0 °C. Add 26.6 g (146 mmol) of N,N'-diethyl-3,5-heptanediimide to prepare a mixture solution. Raise the temperature of the mixture solution to approximately 60 °C and stir at approximately 60 °C for approximately 4 hours. Distill the solvent from the mixture solution to give 28.9 g (83% yield) of the product.

[0196] [Elemental Analysis]

[0197] Al: 11.1% by weight (calculated value 11.3%)

[0198] C: 65.8 wt%, H: 11.3 wt%, N: 11.8 wt% (calculated; C: 65.5%, H: 11.4%, N: 11.8%)

[0199] Nuclear magnetic resonance (NMR) 1 [H-NMR analysis]

[0200] (0.90:s:1H)(3.11:q:4H)(1.91:q:4H)(1.01:t:6H)(0.91:t:6H)(-0.29:s:6H)

[0201] [Thermal Analysis]

[0202] Using a sample of 9,456 mg, the 50% wt% temperature reduction was measured to be approximately 181 °C.

[0203] <Example 4> Preparation of aluminum compound No. 7

[0204] Add 46 mL (83.2 mmol) of trimethylaluminum / toluene solution to a 300 mL four-necked flask and cool the resulting solution to approximately 20 °C. Add 19.8 g (83.2 mmol) of N,N'-disec-butyl-3,5-heptanediimide to the cooled solution to prepare a mixture. Stir the mixture at room temperature (25 °C) for approximately 5 hours. Distill the solvent from the mixture to give 12.9 g (53% yield) of the product.

[0205] [Elemental Analysis]

[0206] Al: 9.6% by weight (calculated value 9.2%)

[0207] C: 68.5 wt%, H: 12.4 wt%, N: 9.5 wt% (calculated; C: 69.3%, H: 12.0%, N: 9.5%)

[0208] Nuclear magnetic resonance (NMR) 1 [H-NMR analysis]

[0209] (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)

[0210] [Thermal Analysis]

[0211] Using a sample of 9,986 mg, the 50% weight reduction in temperature was measured to be approximately 208 °C.

[0212] <Example 5> Preparation of aluminum compound No. 19

[0213] Add 14.3 g (107 mmol) of aluminum chloride and 200 ml of anhydrous toluene to a 100 ml three-necked flask and stir to prepare the first solution. Cool the first solution to approximately 10 °C.

[0214] Prepare a 500 mL three-necked flask, add 20.1 g (107 mmol) of N,N'-diethyl-3,5-heptanediimide and 200 mL of anhydrous toluene, and stir to prepare a second solution. Cool the second solution to approximately 10 °C. Add 65.2 mL (107 mmol) of a solution of n-butyllithium dissolved in n-hexane dropwise to the cooled second solution. Then, raise the temperature of the second solution to room temperature (25 °C) and stir for approximately 2 hours.

[0215] The first solution was added dropwise to the second solution, and the mixture was stirred at room temperature for about 5 hours to prepare a mixed solution. The mixed solution was filtered, and the solvent was distilled and separated to give 15.3 g of intermediate (aluminum compound 47). 1.89 g (6.77 mmol) of the intermediate and 50 mL of anhydrous toluene were added to a three-necked flask and stirred, then cooled to about -30 °C. 19.3 mL (13.5 mmol) of isopropyllithium dissolved in n-pentane was added to the intermediate. The intermediate was then stirred at room temperature for about 3 hours to give the product. The product was filtered, and the solvent was distilled to give 0.78 g (39% yield) of the final product.

[0216] [Elemental Analysis]

[0217] Al: 8.6% by weight (calculated value 9.2%)

[0218] C: 70.5 wt%, H: 11.7 wt%, N: 9.2 wt% (calculated; C: 69.3%, H: 12.0%, N: 9.5%)

[0219] Nuclear magnetic resonance (NMR) 1 [H-NMR analysis]

[0220] (4.37:s:1H)(3.07:q:4H)(1.91:q:4H)(1.46:d:12H)(1.01:t:6H)(0.94:t:6H)

[0221] (0.58:sep:2H)

[0222] [Thermal Analysis]

[0223] Using a sample of 10,371 mg, the 50% wt% reduction in temperature was measured to be approximately 214 °C.

[0224] <Example 6> Preparation of aluminum compound No. 26

[0225] Add 14.3 g (107 mmol) of aluminum chloride and 200 ml of anhydrous toluene to a 100 ml three-necked flask and stir to prepare the first solution. Cool the first solution to approximately 10 °C.

[0226] Prepare a separate 500 mL three-necked flask, add 20.1 g (107 mmol) of N,N'-diethyl-3,5-heptanediimide and 200 mL of anhydrous toluene, and stir to prepare a second solution. Cool the second solution to approximately 0 °C. Add 65.2 mL (107 mmol) of a solution of n-butyllithium dissolved in n-hexane dropwise to the cooled second solution. Raise the temperature of the second solution to room temperature and stir it at room temperature for approximately 2 hours. Add the first solution dropwise to the second solution to prepare a mixture solution. Stir the mixture solution at room temperature for approximately 5 hours. Filter the mixture solution, and distill and separate the solvent to obtain 15.3 g of the intermediate (aluminum compound 47). Add 0.973 g (3.49 mmol) of the intermediate and 50 mL of anhydrous toluene to the three-necked flask and stir.

[0227] Isopropyl magnesium chloride was dissolved in tetrahydrofuran (THF) to prepare an isopropyl magnesium chloride solution. 3.5 mL (3.49 mmol) of the isopropyl magnesium chloride solution was added to the intermediate solution. The intermediate solution was heated to approximately 70 °C and stirred for approximately 5 hours to obtain the product. The solvent was distilled from the product to give 0.54 g (54% yield) of the final product.

[0228] [Elemental Analysis]

[0229] Al: 8.9% by weight (calculated value 9.4%)

[0230] C: 57.9 wt%, H: 10.8 wt%, N: 10.4 wt%, Cl: 11.5 wt% (calculated; C: 58.6%, H: 9.8%, N: 9.8%, Cl: 12.4%)

[0231] Nuclear magnetic resonance (NMR) 1 [H-NMR analysis]

[0232] (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)

[0233] [Thermal Analysis]

[0234] Using a sample of 10,005 mg, the 50% weight reduction in temperature was measured to be approximately 224 °C.

[0235] <Example 7> Preparation of aluminum compound No. 27

[0236] To prepare the first solution, add 8.68 g (65.1 mmol) of aluminum chloride and 100 ml of anhydrous toluene to a 500 ml four-necked flask.

[0237] Prepare a separate 200 mL four-necked flask and add 13.7 g (65.1 mmol) of N,N'-diisopropyl-3,5-heptanediimide and 100 mL of anhydrous toluene, stirring to prepare a second solution. Cool the second solution to approximately 30 °C. Add 42 mL of a solution of n-butyllithium dissolved in n-hexane dropwise to the cooled second solution. Raise the temperature of the second solution to room temperature and stir for approximately 2 hours. Add the first solution dropwise to the second solution to prepare a mixture solution. Stir the mixture solution at room temperature for approximately 18 hours. Filter the mixture solution and distill and separate the solvent to obtain 15.9 g of the intermediate (aluminum compound No. 48).

[0238] 1.72 g (5.60 mmol) of the intermediate and 50 mL of anhydrous toluene were added to a three-necked flask and stirred. The intermediate was cooled to approximately -20 °C. Isopropyl magnesium chloride was dissolved in tetrahydrofuran (THF) to prepare an isopropyl magnesium chloride solution.

[0239] Add 5.60 mL (5.60 mmol) of isopropyl magnesium chloride solution to the intermediate solution. Heat the intermediate solution to approximately 70 °C and stir for approximately 22 hours to obtain the product. Distill the solvent from the product to give 0.70 g (40% yield) of the final product.

[0240] [Elemental Analysis]

[0241] Al: 8.0% by weight (calculated value 8.6%)

[0242] C: 62.0 wt%, H: 9.8 wt%, N: 8.2 wt%, Cl: 12.0 wt% (calculated; C: 61.0%, H: 10.2%, N: 8.9%, Cl: 11.3%)

[0243] Nuclear magnetic resonance (NMR) 1 [H-NMR analysis]

[0244] (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)

[0245] [Thermal Analysis]

[0246] Using a sample of 9,601 mg, the 50% wt% reduction in temperature was measured to be approximately 222 °C.

[0247] <Example 8> Preparation of aluminum compound No. 33

[0248] 26.7 g (200 mmol) of aluminum chloride and 150 mL of anhydrous toluene were added to a 1 L four-necked flask and stirred to prepare a first solution. The first solution was cooled to approximately 20 °C. 30.6 g (600 mmol) of lithium dimethylamino was dissolved in anhydrous toluene to prepare a lithium dimethylamino solution. 300 mL of the lithium dimethylamino solution was added dropwise to the cooled first solution to prepare a mixed solution. The mixed solution was heated to approximately 50 °C and stirred for approximately 7 hours. The mixed solution was filtered, and the solvent was distilled to give 30.6 g of the intermediate. 4.86 g (15.2 mmol) of the intermediate and 100 mL of anhydrous toluene were added to a 200 mL four-necked flask and stirred. Then, 5.54 g (30.4 mol) of N,N'-diethyl-3,5-heptanediimide was added and stirred to give the product. Stirring was carried out at approximately 100 °C for approximately 12 hours. The solvent was distilled from the product to give 4.27 g (yield 47%) of the final product.

[0249] [Elemental Analysis]

[0250] Al: 9.8% by weight (calculated value 9.1%)

[0251] C: 59.2 wt%, H: 11.5 wt%, N: 19.5 wt% (calculated; C: 60.8%, H: 11.2%, N: 18.9%)

[0252] Nuclear magnetic resonance (NMR) 1 [H-NMR analysis]

[0253] (4.47:s:1H)(3.24:q:4H)(2.89:s:12H)(1.96:q:4H)(1.08:t:6H)(0.94:t:6H)

[0254] [Thermal Analysis]

[0255] Using a sample of 9,936 mg, the 50% weight reduction in temperature was measured to be approximately 205 °C.

[0256] <Example 9> Preparation of aluminum compound No. 34

[0257] Add 8.68 g (65.1 mmol) of aluminum chloride and 100 ml of anhydrous toluene to a 500 ml four-necked flask and stir to prepare the first solution.

[0258] Add 13.7 g (65.1 mmol) of N,N'-diisopropyl-3,5-heptanediimide and 100 mL of anhydrous toluene to a 200 mL four-necked flask and stir to prepare a second solution. Cool the second solution to approximately -30 °C. Add 42 mL of a solution of n-butyllithium dissolved in n-hexane dropwise to the second solution, raise the temperature of the second solution to room temperature, and stir for approximately 2 hours. Add the first solution dropwise to the second solution to prepare a mixed solution. Stir the mixed solution at room temperature for approximately 18 hours.

[0259] The mixture was filtered, and the solvent was distilled and separated to obtain 15.8 g of intermediate (compound 48). 1.89 g (6.16 mmol) of the intermediate and 50 mL of anhydrous toluene were added to a three-necked flask and stirred. The intermediate was then cooled to approximately -20 °C. A lithium dimethylaminosol solution was prepared by dissolving 30.6 g (600 mmol) of lithium dimethylaminosol in anhydrous toluene.

[0260] To prepare the intermediate solution, 15 mL of lithium dimethylamino solution was added to the intermediate. The intermediate solution was heated to room temperature and stirred for approximately 6 hours to obtain the product. The product was filtered. The solvent was distilled from the product to give 1.34 g (67% yield) of the final product.

[0261] [Elemental Analysis]

[0262] Al: 9.0% by weight (calculated value 8.3%)

[0263] C: 62.2 wt%, H: 10.2 wt%, N: 18.6 wt% (calculated; C: 62.9%, H: 11.5%, N: 17.3%)

[0264] Nuclear magnetic resonance (NMR) 1 [H-NMR analysis]

[0265] (4.43:s:1H)(3.72:sep:2H)(2.75:s:12H)(2.04:q:4H)(1.30:d:12H)(0.98:t:6H)

[0266] [Thermal Analysis]

[0267] Using a sample of 9,976 mg, the 50% wt% temperature reduction was measured to be approximately 214 °C.

[0268] <Example 10> Preparation of aluminum compound No. 40

[0269] Add 14.3 g (107 mmol) of aluminum chloride and 200 ml of anhydrous toluene to a 500 ml four-necked flask and stir to prepare the first solution. Cool the first solution to approximately 10 °C.

[0270] Add 20.1 g (107 mmol) of N,N'-diethyl-3,5-heptanediimide and 200 ml of anhydrous toluene to a 500 ml three-necked flask and stir to prepare a second solution. Cool the second solution to approximately 0 °C.

[0271] Add 65.2 mL of a solution of n-butyllithium dissolved in n-hexane dropwise to the second solution. Raise the temperature of the second solution to room temperature and stir for approximately 2 hours. Add the first solution dropwise to the second solution to prepare a mixture solution. Stir the mixture solution at room temperature for approximately 5 hours. Filter the mixture solution and distill and separate the solvent to give 15.3 g of the intermediate (compound 47). Add 1.21 g (4.33 mmol) of the intermediate and 10 mL of anhydrous toluene to a three-necked flask and stir to obtain an intermediate solution. Cool the intermediate to approximately -20 °C. Dissolve 0.221 g (4.33 mmol) of dimethylaminolithium in anhydrous toluene to prepare a dimethylaminolithium solution. Add 10 mL of the dimethylaminolithium solution dropwise to the intermediate solution and stir at room temperature for approximately 5 hours to obtain the product. Filter the product. Distill the solvent from the product to give 0.25 g (20% yield) of the final product.

[0272] [Elemental Analysis]

[0273] Al: 10.2% by weight (calculated value 9.4%)

[0274] C: 55.3 wt%, H: 8.5 wt%, N: 13.5 wt%, Cl: 12.5 wt% (calculated; C: 54.3%, H: 9.5%, N: 14.6%, Cl: 12.3%)

[0275] Nuclear magnetic resonance (NMR) 1 [H-NMR analysis]

[0276] (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)

[0277] [Thermal Analysis]

[0278] Using a sample of 10,389 mg, the 50% weight reduction in temperature was measured to be approximately 220 °C.

[0279] <Example 11> Preparation of aluminum compound No. 55

[0280] Add 53.9 ml (97.1 mmol) of trimethylaluminum / toluene solution and 50 ml of anhydrous toluene to a 300 ml four-necked flask, and cool the solution to approximately 10 °C. Add 16.4 g (97.1 mmol) of N-isopropyl-5-imino-3-heptanone to the cooled solution to prepare a mixed solution.

[0281] The temperature of the mixture was raised to room temperature, and the mixture was stirred for about 6 hours. The solvent was removed by distillation of the mixture to obtain 19.5 g (89% yield) of the final product.

[0282] [Elemental Analysis]

[0283] Al: 11.2% by weight (calculated value 12.0%)

[0284] C: 64.7 wt%, H: 9.7 wt%, N: 5.5 wt% (calculated; C: 64.0%, H: 10.7%, N: 6.2%)

[0285] Nuclear magnetic resonance (NMR) 1 [H-NMR analysis]

[0286] (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)

[0287] [Thermal Analysis]

[0288] Using a sample of 9,953 mg, the 50% weight reduction in temperature was measured to be approximately 175 °C.

[0289] <Example 12> Preparation of aluminum compound No. 69

[0290] Add 11.9 g (89.3 mmol) of aluminum chloride and 100 ml of anhydrous toluene to a 300 ml four-necked flask and stir to prepare a first solution. Cool the first solution to approximately 0 °C.

[0291] Add 11.4 g (89.3 mmol) of N-ethyl-4-imino-2-heptanone and 100 ml of anhydrous toluene to a 200 ml four-necked flask and stir to prepare a second solution. Cool the second solution to approximately -40 °C.

[0292] Add 57.4 ml (89.36 mmol) of a solution of n-butyllithium dissolved in n-hexane to the second solution. Raise the temperature of the second solution to room temperature and stir for approximately 2 hours. Add the first solution dropwise to the second solution to prepare a mixture solution. Raise the temperature of the mixture solution to room temperature and stir for approximately 20 hours.

[0293] The mixture was filtered, and the solvent was separated by distillation to give 10.2 g of the intermediate. 1.59 g (7.10 mmol) of the intermediate and 50 mL of anhydrous toluene were added to a three-necked flask and stirred to obtain an intermediate solution. The intermediate solution was cooled to approximately -20 °C. 14.2 mL (7.10 mmol) of isopropyl magnesium chloride was added dropwise to the cooled intermediate solution. The intermediate solution was heated to approximately 50 °C and stirred for approximately 4 hours to obtain the product. The product was filtered. The solvent was distilled from the product to give 0.65 g (38% yield) of the final product.

[0294] [Elemental Analysis]

[0295] Al: 12.2% by weight (calculated value 11.3%)

[0296] C: 64.2 wt%, H: 12.0 wt%, N: 5.3 wt% (calculated; C: 65.2%, H: 11.0%, N: 5.9%)

[0297] Nuclear magnetic resonance (NMR) 1 [H-NMR analysis]

[0298] (4.56:s:1H)(2.87:q:2H)(1.72:s:3H)(1.46:dd:12H)(1.24:s:3H)(0.82:t:3H)

[0299] (0.60:sep:2H)

[0300] [Thermal Analysis]

[0301] Using a sample of 10,228 mg, the 50% wt% temperature reduction was measured to be approximately 177 °C.

[0302] <Comparative Example 1>

[0303] An aluminum compound represented by formula 4A was prepared as a comparative example.

[0304] [Formula 4A]

[0305]

[0306] <Comparative Example 2>

[0307] An aluminum compound represented by formula 4B was prepared as a comparative example.

[0308] [Formula 4B]

[0309]

[0310] <Comparative Example 3>

[0311] An aluminum compound represented by formula 4C was prepared as a comparative example.

[0312] [Formula 4C]

[0313]

[0314] Table 1 shows the evaluation results of the auto-ignition properties of the aluminum compounds in the experimental and comparative examples. The auto-ignition properties are the observation results of the aluminum compounds igniting after being left to stand in the atmosphere.

[0315] [Table 1]

[0316] Spontaneous combustion properties Comparative Example 1 Observed Comparative Example 2 none Comparative Example 3 none Experimental Example 1 none Experiment Example 2 none Experimental Example 3 none Experiment Example 4 none Experimental Example 5 none Experimental Example 6 none Experimental Example 7 none Experimental Example 8 none Experimental Example 9 none Experimental Example 10 none Experimental Example 11 none Experimental Example 12 none

[0317] Referring to Table 1, the aluminum compound of Comparative Example 1 exhibits spontaneous combustion properties. The aluminum compound of Comparative Example 1 is unstable in the atmosphere and may be difficult to use as a deposition precursor. The aluminum compounds of Experimental Examples 1 to 12 did not exhibit spontaneous combustion properties. The aluminum compounds of Experimental Examples 1 to 12 can be used as deposition precursors.

[0318] Table 2 shows the measurement results of melting point and thermal decomposition temperature for Experimental Examples 1 to 12, Comparative Example 2, and Comparative Example 3. Melting point was observed at approximately 1,103 Pa and approximately 30 °C. Thermal decomposition temperature was measured using a differential scanning calorimeter.

[0319] [Table 2]

[0320] Melting point Thermal decomposition temperature Comparative Example 2 Below 30℃ 190℃ Comparative Example 3 80℃ 350℃ Experimental Example 1 40℃ 380℃ Experiment Example 2 Below 30℃ 390℃ Experimental Example 3 Below 30℃ 390℃ Experiment Example 4 Below 30℃ 400℃ Experimental Example 5 Below 30℃ 390℃ Experimental Example 6 Below 30℃ 410℃ Experimental Example 7 Below 30℃ 400℃ Experimental Example 8 Below 30℃ 350℃ Experimental Example 9 Below 30℃ 350℃ Experimental Example 10 Below 30℃ 400℃ Experimental Example 11 Below 30℃ 320℃ Experimental Example 12 Below 30℃ 310℃

[0321] Referring to Table 2, Comparative Example 2 has a low thermal decomposition temperature. The thermal decomposition temperature of the aluminum compound in Comparative Example 2 can be below about 300°C. When using the aluminum compound of Comparative Example 2 as a deposition precursor, some limitations may be imposed on the deposition process due to its low thermal stability. For example, the deposition window (ALD window) may be narrow. The aluminum compounds of Experimental Examples 1 to 12 can have higher thermal decomposition temperatures of about 300°C to about 600°C. The aluminum compounds of Experimental Examples 1 to 12 can have excellent thermal stability. Therefore, when using the aforementioned aluminum compounds as deposition precursors, limitations on the deposition process can be reduced. For example, the deposition process can be performed with a wider deposition window range.

[0322] The deposition precursor can be transported in a liquid state. If the melting point of the deposition precursor increases, the preparation of the liquid deposition precursor may become difficult. Comparative Example 3 can have a high melting point. For example, the melting point of Comparative Example 3 can be about 80°C. Therefore, when using the aluminum compound of Comparative Example 3 as the deposition precursor, the transport of the deposition precursor may become difficult. The aluminum compounds of Experimental Examples 1 to 12 can have a low melting point (e.g., a melting point below 45°C). Therefore, when using the aluminum compounds of Experimental Examples 1 to 12 as the deposition precursor, the transport of the deposition precursor can be easy.

[0323] Figure 8 This shows the results of film deposition thickness per cycle, based on temperature. Film deposition processes were performed using each of the deposition precursors from Comparative Example 1 and Experimental Example 3. The horizontal axis represents the substrate temperature. Films were deposited by performing an atomic layer deposition process, and the thickness of the film deposited per cycle represents the deposition rate.

[0324] Reference Figure 8 Under the same temperature conditions, the thickness (c) of the film deposited using Comparative Example 1 is greater than the thickness (e) of the film deposited using Experimental Example 3. The deposition process using the aluminum compound according to the exemplary embodiment has a slow deposition rate, and the thickness of the deposited film can be reduced. For example, when using Experimental Example 3 as the deposition precursor, the thickness (e) of the film deposited in each cycle is approximately... to approximately

[0325] According to one aspect of the invention, the aluminum compound has a low melting point and can be easily transported. The aluminum compound can be used as a deposition precursor. The aluminum compound can exhibit excellent stability. The deposition process can have a wide deposition window. By using the deposition process with the deposition precursor, a thin film can be formed. The thin film can exhibit improved properties.

[0326] Although exemplary embodiments of the inventive concept have been described, it should be understood that the inventive concept is not limited to these exemplary embodiments, and various changes and modifications can be made by those skilled in the art within the spirit and scope of the inventive concept as claimed in the appended claims.

Claims

1. An aluminum compound represented by Formula 1: [Formula 1] wherein In Formula 1, one of R 1 and R 2 is dimethylamino, the other is Cl, Z is N-R 7 , R 3 is hydrogen, R 4 and R 7 are each independently any one selected from the group consisting of methyl, ethyl, and isopropyl, and R 5 and R 6 are each independently any one selected from the group consisting of methyl and ethyl.

2. The aluminum compound of claim 1, wherein, In Formula 1, R 1 is dimethylamino.

3. The aluminum compound of claim 1, wherein, In Formula 1, R 2 is dimethylamino.

4. A method for manufacturing a semiconductor device, comprising: preparing a deposition precursor including an aluminum compound; and forming a thin film using the deposition precursor, wherein the aluminum compound is represented by the following Formula 1: [Formula 1] ， wherein, in Formula 1, R 1 and one of R 2 is dimethylamino, the other is Cl, Z is N-R 7 , R 3 is hydrogen, R 4 and R 7 are each independently any one selected from the group consisting of methyl, ethyl, and isopropyl, and R 5 and R 6 are each independently any one selected from the group consisting of methyl and ethyl.

5. The method for manufacturing a semiconductor device of claim 4, wherein a thickness of the thin film deposited per cycle is 0.05 Å to 0.6 Å.

6. The method for manufacturing a semiconductor device of claim 4, wherein the forming a thin film further comprises: supplying the deposition precursor into a chamber to form a precursor layer on a substrate; and supplying a reaction gas on the precursor layer.

7. The method for manufacturing a semiconductor device of claim 6, wherein the supplying a reaction gas comprises supplying the reaction gas into the chamber, wherein a temperature of the chamber when the deposition precursor is supplied is 300 °C to 600 °C, and wherein a temperature of the chamber when the reaction gas is supplied is 300 °C to 600 °C.

8. The method for manufacturing a semiconductor device of claim 4, wherein the forming a thin film is performed a plurality of times, and wherein the thin film includes a plurality of stacked thin films.

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