Novel metal precursor for forming thin film using cyclopentadiene and method for manufacturing same

Abstract

Disclosed are a novel metal precursor for forming a thin film using cyclopentadiene and a method for manufacturing same. The method for preparing a metal precursor according to the present invention comprises the steps of: (a) adding a C4-C6 alkyl group (R1))-halogen (X) compound to cyclopentadiene (CP) to form a first compound represented by Cp-R1; (b) adding an alkali metal compound and a first organic solvent to the first compound represented by Cp-R1, and then adding a halogen (X)-metal (M) compound and a second organic solvent to form a second compound represented by M(Cp-R1)3-yXy (y = 0 or 1); and preparing a metal precursor by adding a third organic solvent and ligand to the second compound represented by M(Cp-R1)3-yXy, wherein in the halogen (X)-metal (M) compound, the metal (M) is yttrium (Y).

Description

A novel metal precursor for forming thin films using cyclopentadiene and a method for producing the same

[0001] The present invention relates to a novel metal precursor for forming a thin film using cyclopentadiene and a method for producing the same.

[0002] The research subject information of the present invention is as follows.

[0003] [Detailed Project Number]: 1415186019, [Project Number]: 20010460, [Ministry Name]: Ministry of Trade, Industry and Energy, [Project Management Agency]: Korea Institute of Industrial Technology Evaluation and Planning, [Research Project Name]: Development of Strategic Core Material Self-Reliance Technology, [Research Project Name]: Development of Highly Corrosion-Resistant Ceramic ALD Precursor and Core Components for High-Direct Semiconductor Deposition and Etching Process Equipment, [Project Implementing Organization Name]: LK Chem Co., Ltd., Host Organization: Point Engineering Co., Ltd., [Research Period]: April 1, 2020 - December 31, 2024

[0004] A variety of precursors have been used to fabricate thin films, and a variety of deposition techniques have been employed. These include reactive sputtering, ion-assisted deposition, sol-gel deposition, chemical vapor deposition (CVD) (also known as metal-organic CVD or MOCVD), and atomic layer deposition (ALD) (also known as atomic layer epitaxy).

[0005] Among these, CVD and ALD processes are mainly used because they have improved composition control, high film uniformity, and effective doping control.

[0006] Chemical vapor deposition (CVD) is a chemical process that uses precursors to form thin films on a substrate surface. In a typical CVD process, precursors are passed over the surface of a substrate (e.g., a wafer) within a low-pressure or ambient-pressure reaction chamber. The precursors react or decompose on the substrate surface, forming a thin film of the deposited material. Volatile byproducts are removed by a gas flow through the reaction chamber. Controlling the thickness of the deposited film can be difficult because it depends on many parameters, such as temperature, pressure, gas flow volume and uniformity, chemical depletion effects, and timing.

[0007] Atomic layer deposition (ALD) is also a method for depositing thin films. ALD is a surface reaction-based film growth technique that provides precise thickness control and can deposit conformal thin films of a precursor-derived material onto substrates of varying composition. In ALD, precursors separate during the reaction. A first precursor passes over the substrate surface, forming a monolayer on the substrate surface. Any excess unreacted precursor is pumped out of the reaction chamber. A second precursor is then passed over the substrate surface and reacts with the first precursor, forming a second monolayer of film on the first monolayer of film on the substrate surface. This cycle is repeated to form a film of the desired thickness.

[0008] Thin films, especially metal-containing thin films, have several important applications, for example in nanotechnology and the fabrication of semiconductor devices.

[0009] In this regard, yttrium-containing oxide films or lanthanide-metal-containing oxide films are being studied as gate dielectric materials for field-effect transistors in semiconductor devices due to their various properties, such as a wide bandgap (5.6 eV), low leakage current, high breakdown voltage, and good thermal stability. In addition, yttrium-containing oxide films or lanthanide metal-containing oxide films are being studied as gate insulators for DRAMs among semiconductor memory devices, high-k dielectric layers for capacitors, and as insulators for metal-insulator-metal (MIM) structures for nonvolatile resistive switching memory devices.

[0010] Most of the yttrium or lanthanide metal precursor compounds known to date have low vapor pressures and are solids or highly viscous liquids. Therefore, they are disadvantageous for use as precursors in the mass production of semiconductor devices when forming oxide films containing yttrium or lanthanide metals by chemical vapor deposition (CVD) or atomic layer deposition (ALD). In order to form yttrium or lanthanide metal-containing films required for the manufacture of next-generation semiconductor devices by ALD, precursor compounds with lower viscosity or higher vapor pressure than the existing yttrium precursor compounds or lanthanide metal precursor compounds are required.

[0011] The purpose of the present invention is to provide a method for producing a novel metal precursor for forming a thin film, which can stably produce a metal (yttrium (Y)) precursor using a novel cyclopentadiene ligand under mild conditions using water as a solvent.

[0012] In addition, it is an object of the present invention to provide a method for producing a metal precursor having excellent deposition characteristics by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

[0013] The objectives of the present invention are not limited to those mentioned above. Other objectives and advantages of the present invention not mentioned above can be understood through the following description and will be more clearly understood through the embodiments of the present invention. Furthermore, it will be readily apparent that the objectives and advantages of the present invention can be realized by the means and combinations thereof set forth in the claims.

[0014] The method for producing a metal precursor according to the present invention comprises the steps of (a) adding a C4 to C6 alkyl group (R1)-halogen (X) compound to cyclopentadiene (Cp) to form a first compound represented by Cp-R1; (b) adding an alkali metal compound and a first organic solvent to the first compound represented by Cp-R1, and then adding a halogen (X)-metal (M) compound and a second organic solvent to form M(Cp-R1). 3-y X y (y = 0 or 1) forming a second compound represented by; and (c) the M(Cp-R1) 3-y X y A step of preparing a metal precursor by adding a third organic solvent and a ligand to a second compound represented by , wherein in the halogen (X)-metal (M) compound, the metal (M) is yttrium (Y).

[0015] The step (a) includes: (a1) forming a mixture by mixing purified water and an alkali metal compound; and (a2) adding cyclopentadiene (Cp) to the mixture, and then adding a C4 to C6 alkyl group (R1)-halogen (X) compound and an organic solvent to form a first compound represented by Cp-R1; wherein the molar number of the purified water in the step (a1) is greater than the molar number of the cyclopentadiene (Cp) in the step (a2), and the purified water in the step (a1) and the organic solvent in the step (a2) are mixed in a weight ratio of 1:0.5 to 1.0, and in the step (a2), the cyclopentadiene (Cp) and the C4 to C6 alkyl group (R1)-halogen (X) compound can be mixed in a molar ratio of 1:0.8 to 1.1.

[0016] In the step (b) above, the first compound represented by Cp-R1: alkali metal compound may be mixed in a molar ratio of 1:1.0 to 1.2, and in the step (b), 400 to 600 mL of diethyl ether, which is a first organic solvent, may be mixed with respect to 0.9 mol of the alkali metal compound, and in the step (b), 400 to 600 mL of diethyl ether, which is a second organic solvent, may be mixed with respect to 0.232 mol of the halogen (X)-metal (M) compound.

[0017] In the above step (c), the ligand may include N,N'-diisopropylpropionimidamide [(CH3)2CHNC(CH2CH3)NHCH(CH3)2].

[0018] In the above step (c), M(Cp-R1) 3-y X y For 30 g of the second compound represented by , 50 to 200 mL of normal-hexane, a third organic solvent, can be mixed.

[0019] The alkali metal compound may include at least one of KOH, NaNH2, CH3ONa, NaH, and NaOH, and the halogen (X) may include one of Cl, Br, and I.

[0020] The above M(Cp-R1) 3-y X y The second compound represented by: Ligand can be mixed in a molar ratio of 1:0.5 to 1.5.

[0021] The metal precursor according to the present invention is characterized in that it is manufactured by the method for manufacturing the metal precursor.

[0022]

[0023] The method for manufacturing a metal film according to the present invention is characterized in that deposition is performed using the metal precursor by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

[0024] The method for producing a novel metal precursor for forming a thin film according to the present invention has the effect of stably producing a novel metal precursor containing yttrium (Y) under mild conditions using water as a solvent.

[0025] Accordingly, there is an effect of increasing the yield of the compound synthesized at each stage.

[0026] Additionally, it has excellent deposition characteristics by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

[0027] In addition to the effects described above, specific effects of the present invention are described below while explaining specific details for carrying out the invention.

[0028] Figure 1 shows NMR data for sec-butylcyclopentadiene.

[0029] Figure 2 shows NMR data for tris(n-butylcyclopentadienyl)yttrium.

[0030] Figure 3 shows TGA data for tris(n-butylcyclopentadienyl)yttrium.

[0031] Figure 4 shows DSC data for tris(n-butylcyclopentadienyl)yttrium.

[0032] Figure 5 shows NMR data for tris(sec-butylcyclopentadienyl)yttrium.

[0033] Figure 6 shows TGA data for tris(sec-butylcyclopentadienyl)yttrium.

[0034] Figure 7 shows DSC data for tris(sec-butylcyclopentadienyl)yttrium.

[0035] Figure 8 shows NMR data for bis(n-butylcyclopentadienyl)(N,N'-diisopropyl-ethylamidinate)yttrium.

[0036] Figure 9 shows NMR data for bis(sec-butylcyclopentadienyl)(N,N'-diisopropyl-ethylamidinate)yttrium.

[0037] Figure 10 is a graph for Table 1.

[0038] Figure 11 is a graph for Table 2.

[0039] Figure 12 is a graph for Table 3.

[0040] The above-described objects, features, and advantages will be described in detail below with reference to the accompanying drawings, so that those skilled in the art can easily practice the technical idea of ​​the present invention. In describing the present invention, if it is determined that a detailed description of known technologies related to the present invention may unnecessarily obscure the gist of the present invention, a detailed description thereof will be omitted. Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the drawings, the same reference numerals are used to indicate the same or similar components.

[0041] Hereinafter, the phrase "any configuration is placed on (or below)" a component or "on (or below)" a component may mean that any configuration is placed in contact with the upper surface (or lower surface) of said component, and that other configurations may be interposed between said component and any configuration placed on (or below) said component.

[0042] Additionally, when it is described that a component is "connected," "coupled," or "connected" to another component, it should be understood that the components may be directly connected or connected to one another, but that other components may also be "interposed" between the components, or that each component may be "connected," "coupled," or "connected" through another component.

[0043] Hereinafter, a novel metal precursor for forming a thin film using cyclopentadiene and a method for producing the same according to some embodiments of the present invention will be described.

[0044] The present inventors have confirmed that a novel metal precursor for forming a thin film based on cyclopentadiene can be stably prepared under mild conditions using water as a solvent.

[0045] In addition, the inventors of the present invention have confirmed through experiments that, in the process of manufacturing a metal precursor containing two or more ligands, a metal precursor having excellent deposition characteristics can be manufactured by chemical vapor deposition (CVD) or atomic layer deposition (ALD) without using an alkali metal compound.

[0046] The metal precursor comprising cyclopentadiene and a ligand manufactured in the present invention has excellent heat resistance and volatility along with deposition characteristics, has high yield and high purity, and can exhibit performance required for manufacturing next-generation devices such as semiconductors, and thus has advantageous advantages in forming a metal film or a metal-containing thin film.

[0047] The metal precursor of the present invention is manufactured according to the manufacturing method of the present invention, and refers to a metal-containing molecule or compound that can be used to manufacture a metal film or a metal-containing thin film by a vapor deposition process such as ALD or CVD. The metal precursor can be deposited, adsorbed, decomposed, transferred, or / and passed through a substrate or its surface, thereby manufacturing a metal film or a metal-containing thin film.

[0048] The term "cyclopentadiene" refers to a five-membered cyclic hydrocarbon C5H6 with a conjugated double bond within the ring, also called a cyclopentadienyl group.

[0049] The term "ligand" refers to an ion or molecule that surrounds and coordinates a central atom in a complex, also called a ligand.

[0050] The term "alkyl" (alone or in combination with another term(s)) refers to a saturated hydrocarbon chain of from 4 to about 6 carbon atoms in length, such as, but not limited to, butyl, pentyl, hexyl, and the like. Alkyl groups can be straight or branched. An "alkyl group" includes alkyl groups in all structural isomeric forms. For example, propyl includes one or more of n-propyl and isopropyl, butyl includes one or more of n-butyl, sec-butyl, isobutyl, and tert-butyl, and pentyl includes one or more of n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, and 3-pentyl. Furthermore, as used herein, "Me" refers to methyl, "Et" refers to ethyl, "Pr" refers to propyl, "i-Pr" refers to isopropyl, "Bu" refers to butyl, "t-Bu" refers to tert-butyl, "iBu" refers to isobutyl, "Pn" refers to pentyl, and "NPn" refers to neopentyl.

[0051] The method for producing a metal precursor according to the present invention comprises the steps of (a) adding a C4 to C6 alkyl group (R1)-halogen (X) compound to cyclopentadiene (Cp) to form a first compound represented by Cp-R1, (b) adding an alkali metal compound and a first organic solvent to the first compound represented by Cp-R1, and then adding a halogen (X)-metal (M) compound and a second organic solvent to form M(Cp-R1). 3-y X y(y = 0 or 1) forming a second compound, and (c) the M(Cp-R1) 3-y X y It is characterized by including a step of preparing a metal precursor by adding a third organic solvent and a ligand to a second compound represented by .

[0052] (a) The step of forming a first compound, which is a ligand represented by Cp-R1, by adding a C4 to C6 alkyl group (R1)-halogen (X) compound to cyclopentadiene (Cp) can be performed according to Synthetic Formula 1.

[0053] [Synthesis Formula 1]

[0054]

[0055] First, (a1) a step of mixing purified water and an alkali metal compound (B) to form a mixture may be included. In the present invention, purified water can be used instead of an organic solvent to stably synthesize the final product, a novel metal precursor for forming a thin film. In particular, by utilizing the difference in solubility in water, the first compound, which is a ligand, can be formed without an extraction step using an organic solvent.

[0056] The alkali metal compound (B) may include at least one of KOH, NaNH2, CH3ONa, NaH, and NaOH, and preferably may include at least one of KOH and NaNH2.

[0057] Purified water and an alkali metal compound (B) can be mixed in a weight ratio of 1:0.1 to 0.5, and preferably in a weight ratio of 1:0.2 to 0.3. Since the purified water and the alkali metal compound satisfy a weight ratio of 1:0.1 to 0.5, there is an advantage in forming a first compound, which is a ligand.

[0058] Next, (a2) a step of adding cyclopentadiene (Cp) to the mixture, and then adding a C4 to C6 alkyl group (R1)-halogen (X) compound and an organic solvent to form a first compound, which is a ligand represented by Cp-R1.

[0059] In the C4 to C6 alkyl group (R1)-halogen (X) compound, the C4 to C6 alkyl group (R1) may be -CH2CH2CH2CH3, -CH(CH3)CH2CH3, -CH2CH(CH3)2, or -C(CH3)3. C5 may be -CH2CH2CH2CH2CH3, -CH(CH3)CH2CH2CH3, -CH(CH2CH3)2, -CH2CH(CH3)CH2CH3, -CH2CH2CH(CH3)2, -C(CH3)2CH2CH3, -CH(CH3)CH(CH3)2, or -CH2C(CH3)3. C6 may be -CH2CH2CH2CH2CH2CH 3, -CH(CH3)CH2CH2CH2CH 3, -CH(CH2CH3)CH2CH2CH 3, -CH2CH2CH2CH(CH3) 2, -CH(CH3)CH2CH(CH3) 2, -CH(CH2CH3)CH(CH3) 2, -CH2CH(CH3)CH2CH2CH3, -CH2CH2CH(CH3)CH2CH 3, -C(CH2CH3)2CH 3, -CH2CH(CH2CH3) 2, -CH(CH3)CH(CH3)CH2CH 3, -CH2CH2C(CH3) 3, -CH2C(CH3)2CH2CH 3, -CH(CH3)C(CH3)3, -C(CH3)2CH(CH3)2, or -CH2CH(CH3)CH(CH3)2.

[0060] In a C4 to C6 alkyl group (R1)-halogen (X) compound, the halogen (X) may include one of Cl, Br, and I, and preferably may include Br.

[0061] The organic solvent may include one or more of dimethyl sulfoxide (DMSO), dimethylformamide (DMF), diethyl ether, normal hexane, and hexamethylphosphoramide (HMPA).

[0062] At this time, the purified water of (a1) and the organic solvent of (a2) can be mixed in a weight ratio of 1:0.5 to 1.5, and preferably in a weight ratio of 1:0.5 to 1.0.

[0063] In addition, the purified water of (a1) and the cyclopentadiene (Cp) of (a2) can be mixed in a molar ratio of 2 to 5:1, and preferably in a molar ratio of 3 to 4:1.

[0064] In addition, in step (a2), the cyclopentadiene (Cp): C4 to C6 alkyl group (R1)-halogen (X) compound can be mixed in a molar ratio of 1:0.5 to 1.5, and preferably in a molar ratio of 1:0.8 to 1.1.

[0065] In this way, in the step of forming the first compound represented by Cp-R1, by using purified water in an amount greater than the respective amounts of the organic solvent and cyclopentadiene (Cp), and satisfying the molar ratio of cyclopentadiene (Cp): C4 to C6 alkyl group (R1) - halogen (X) compound of 1:0.5 to 1.5, the first compound, which is the ligand, can be stably synthesized, and high purity and high efficiency can be secured. If an excess of cyclopentadiene is used compared to the purified water amount, the yield may decrease due to unreacted cyclopentadiene remaining.

[0066] The step of forming a first compound represented by Cp-R1 by adding a C4 to C6 alkyl group (R1)-halogen (X) compound to cyclopentadiene (Cp) can be performed at 0 to room temperature (25±2)°C, and preferably, the reaction can be performed at 0 to 10°C. The first compound, which is a ligand represented by alkyl-cyclopentadiene, can exhibit a liquid phase.

[0067] (b) After adding an alkali metal compound and a first organic solvent to the first compound represented by Cp-R1, a halogen (X)-metal (M) compound and a second organic solvent are added to obtain M(Cp-R1) 3-y X y The step of forming the second compound represented by (y = 0 or 1) can be performed according to synthetic formula 2.

[0068] [Synthesis Formula 2]

[0069]

[0070] (b) In step (b), the first compound represented by Cp-R1: alkali metal compound (B) can be mixed in a molar ratio of 1:1.0 to 1.5, and preferably in a molar ratio of 1:1.0 to 1.2. Since the first compound: alkali metal compound (B) satisfies a molar ratio of 1:1.0 to 1.5, there is an advantage in forming the second compound.

[0071] The first organic solvent may include at least one of dimethyl sulfoxide (DMSO), dimethylformamide (DMF), diethyl ether, normal hexane, and hexamethylphosphoramide (HMPA), and preferably may include diethyl ether.

[0072] Additionally, for 0.9 mol of the alkali metal compound, 400 to 600 mL of diethyl ether, which is the first organic solvent, can be mixed, preferably 450 to 550 mL can be mixed, and more preferably 500 mL can be mixed.

[0073] By mixing 400 to 600 mL of diethyl ether, the first organic solvent, with respect to 0.9 mol of an alkali metal compound, the synthetic reaction can proceed more smoothly at a dilute concentration.

[0074] In addition, an alkali metal compound and a first organic solvent may be added to the first compound represented by Cp-R1 to form an intermediate. Here, the intermediate is formed by a reaction between the first compound represented by Cp-R1 and the alkali of the alkali metal compound, and may include, for example, normal-butyl cyclopentadienyl sodium, sec-butyl cyclopentadienyl sodium, etc. The yield of such an intermediate may be 80% or more, and preferably 85% or more.

[0075] The above intermediate may exhibit a solid phase.

[0076] In a halogen (X)-metal (M) compound, the metal (M) may include yttrium (Y).

[0077] The second organic solvent may include at least one of dimethyl sulfoxide (DMSO), dimethylformamide (DMF), diethyl ether, normal hexane, and hexamethylphosphoramide (HMPA), and preferably may include diethyl ether.

[0078] For 0.232 mol of the halogen (X)-metal (M) compound, 400 to 600 mL of diethyl ether, a second organic solvent, can be mixed, preferably 450 to 550 mL, and more preferably 500 mL.

[0079] And the intermediate formed by adding an alkali metal compound and a first organic solvent to the first compound represented by Cp-R1: halogen (X)-metal (M) compound can be mixed in a molar ratio of 1.5 to 4:1, and preferably in a molar ratio of 1.5 to 3:1.

[0080] When the content of the intermediate is greater than that of the halogen (X)-metal (M) compound, M(Cp-R1) 3-y X y It has the advantage of stably forming a second compound represented by .

[0081] After adding an alkali metal compound and a first organic solvent to the first compound represented by Cp-R1, a halogen (X)-metal (M) compound and a second organic solvent are added to obtain M(Cp-R1) 3-y X y The step of forming the second compound represented by (y = 0 or 1) can be performed at 0 to 35°C, and preferably, the reaction can be performed at 20 to 35°C.

[0082] M(Cp-R1) 3-y X y The second compound represented by may exhibit a liquid phase.

[0083] (c) M(Cp-R1) 3-y X y The step of preparing a metal precursor by adding a third organic solvent and a ligand to a second compound represented by can be performed according to Synthetic Formula 3.

[0084] [Synthesis Formula 3]

[0085]

[0086] In the synthetic formula 3, the third organic solvent may include at least one of dimethyl sulfoxide (DMSO), dimethylformamide (DMF), diethyl ether, normal hexane, and hexamethylphosphoramide (HMPA), and preferably normal hexane.

[0087] M(Cp-R1) 3-y X y For 30 g of the second compound represented by , 50 to 200 mL of normal-hexane, which is a third organic solvent, can be mixed, preferably 80 to 150 mL, and more preferably 100 mL.

[0088] or M(Cp-R1) 3-y X yFor 0.066 mol of the second compound represented by , 50 to 200 mL of normal-hexane, which is a third organic solvent, can be mixed, preferably 80 to 150 mL can be mixed, and more preferably 100 mL can be mixed.

[0089] In the synthetic formula 3, a novel metal precursor for forming a thin film can be prepared by adding a ligand represented by R2NCR3NHR2, and in R2NCR3NHR2, R2 is a C3 to C11 alkyl group, which may be -CH(CH3)CH2CH3, -C(CH3)3, -CH(CH2CH3)2, -CH(CH2CH2CH3)2, -CH(CH2CH2CH2CH2CH3)2 or -CH(CH3)CH2CH2CH3, and R3 is a C1 to C4 alkyl group, which may be -CH3, -CH2CH3, -CH2CH2CH3 or -CH2CH2CH2CH3.

[0090] Preferably, the ligand may include N,N'-diisopropylpropionimidamide [(CH3)2CHNC(CH2CH3)NHCH(CH3)2].

[0091] Also M(Cp-R1) 3-y X y The second compound represented by: ligand can be mixed in a molar ratio of 1:0.5 to 1.5, and preferably in a molar ratio of 1:0.8 to 1.2.

[0092] M(Cp-R1) 3-y X y The step of preparing a metal precursor by adding a third organic solvent and a ligand to a second compound represented by may be performed at 10 to 35°C, and preferably at 20 to 30°C.

[0093] In this way, by satisfying the contents of the third organic solvent and the ligand within the above range with respect to the contents of the second compound, a novel metal precursor for forming a thin film based on cyclopentadiene can be stably manufactured.

[0094] The manufactured metal precursor may be liquid and contain two or more ligands, and may be mixed with various components to form a composition.

[0095] The metal precursor containing yttrium (Y) according to the present invention is characterized in that it is manufactured by a method for manufacturing a metal precursor.

[0096] The method for manufacturing a metal film according to the present invention is characterized in that deposition is performed by chemical vapor deposition (CVD) or atomic layer deposition (ALD) using the metal precursor. Applications of the metal film or thin film include, for example, high-k capacitor films for semiconductors, gate insulating films for semiconductors, ferroelectric capacitor films for semiconductors, and superconductor thin films using oxide ceramics; for example, barrier layers for semiconductors using nitride ceramics; and for example, optical glass for optical fibers, optical waveguides, optical amplifiers, and optical switches using glass.

[0097] The thickness of such metal film or thin film may be 0.1 to 100 μm, preferably 1 to 50 μm, but is not limited thereto.

[0098] Hereinafter, specific examples of a novel metal precursor for forming a thin film using cyclopentadiene and a method for manufacturing the same will be examined.

[0099] [Synthesis Formula 1]

[0100]

[0101] Example 1: Method for producing normal-butylcyclopentadiene

[0102] In a reaction vessel capable of mechanical stirring and maintaining a low temperature, 300 g of purified water was added, then 88.1 g (1.57 mol) of KOH (alkali metal (B)) was slowly added, and after the KOH was completely dissolved, 300 g of DMSO was added. After the mixture was cooled, 80 g (1.21 mol) of cyclopentadiene was slowly added, and the internal temperature was maintained at 10°C or lower for 3 hours. While maintaining the internal temperature of the mixture at 0°C or lower, a solution of 165.8 g (1.21 mol) of 1-bromobutane (R1-X) / 165.8 g of DMSO was slowly added. After the addition was completed, the temperature was raised to 20°C, and the mixture was stirred for 5 hours to complete the reaction. 300 g of purified water was added to the reaction vessel, and the organic layer and aqueous layer were separated. Only the organic layer was collected and filtered through Celite. The filtrate was distilled under reduced pressure to obtain 78 g (0.63 mol, yield 52%) of normal-butylcyclopentadiene.

[0103] Example 2: Method for producing sec-butylcyclopentadiene

[0104] In a reaction vessel capable of mechanical stirring and maintaining a low temperature, 300 g of purified water was added, then 88.1 g (1.57 mol) of KOH (alkali metal (B)) was slowly added, and after the KOH was completely dissolved, 300 g of DMSO was added. After the mixture was cooled, 80 g (1.21 mol) of cyclopentadiene was slowly added, and the internal temperature was maintained at 10°C or lower for 3 hours. While maintaining the internal temperature of the mixture at 0°C or lower, a solution of 165.8 g (1.21 mol) of 2-bromobutane (R1-X) / 165.8 g of DMSO was slowly added. After the addition was completed, the temperature was raised to 20°C, and the mixture was stirred for 5 hours to complete the reaction. 300 g of purified water was added to the reaction vessel, the organic layer and the aqueous layer were separated, and only the organic layer was collected and filtered with Celite. The filtrate was distilled under reduced pressure to obtain 79.6 g (0.65 mol, yield 53%) of sec-butylcyclopentadiene.

[0105] 1H-NMR (400 MHz, C6D6): δ 5.924~6.503 (m, 3H, Cp-H), δ 2.726 (m, 2H, C=C-CH2-C=C), δ 1.481 (m, 2H, Cp-C-CH2), δ 1.077 (d, 3H, C-CH3), δ 0.825 (t, 3H, Cp-CC-CH3)

[0106] Figure 1 shows NMR data for sec-butylcyclopentadiene.

[0107] [Synthesis Formula 2]

[0108]

[0109] Example 3-1: Method for preparing normal-butylcyclopentadienyl sodium

[0110] A reflux device and a mechanical stirrer were installed in a dried 2 L flask. 35.1 g (0.9 mol) of sodium amide NaNH2 (alkali metal (B)) and 500 ml of dried diethyl ether were added to the flask and stirred using a mechanical stirrer. 100 g (0.81 mol) of normal-butylcyclopentadiene (Cp-R1 of Example 1) was slowly added dropwise to the flask. At this time, the reaction temperature did not exceed 35°C, and ammonia was confirmed through a bubbler. The mixture was reacted at room temperature for 15 hours to completion, and 106.9 g (0.736 mol, yield 90%) of normal-butylcyclopentadienyl sodium was obtained through filtration and distillation under reduced pressure.

[0111] Example 3-2: Method for preparing tris(n-butylcyclopentadienyl)yttrium

[0112] A reflux device and a magnetic stirrer were installed in a dried 2 L flask. 47.8 g (0.245 mol) of YCl3(MX3) and 500 mL of dried diethyl ether were added to the flask and stirred with a stirrer. A mixture of 106.9 g (0.736 mol) of normal-butylcyclopentadienyl sodium dissolved in 500 mL of dried diethyl ether was slowly added dropwise to the flask. The reaction temperature did not exceed 35°C, and the reaction was completed after 15 hours. The reaction solution was filtered and distilled under reduced pressure to obtain 55.9 g (0.122 mol, yield 50%) of a yellow liquid compound tris(normal-butylcyclopentadienyl)yttrium.

[0113] 1 H-NMR (400 MHz, C6D6): δ 6.026~6.219 (12H, m, Cp-H), δ 2.427 (m, 3H, Cp-CH2), δ 1.418 (m, 6H, Cp-C-CH2), δ 1.240 (m, 6H, Cp-CC-CH2), δ 0.874 (t, 9H, C-CH3),

[0114] Figure 2 shows NMR data for tris(n-butylcyclopentadienyl)yttrium.

[0115] Figure 3 shows TGA data for tris(n-butylcyclopentadienyl)yttrium, and Figure 4 shows DSC data.

[0116] TGA stands for thermogravimetric analysis. It monitors the weight change of a sample over a period of time when the temperature is changed. It can be used to analyze the composition and decomposition processes of multicomponent samples, as well as perform qualitative analysis. DSC stands for differential scanning calorimetry. It measures the heat input and output of a sample by simultaneously heating and cooling a sample and a reference material.

[0117] Referring to Fig. 3, under the conditions of a heating rate of 10°C / min and a sample amount of 16.614 mg, the temperature at which the mass was reduced by 50% was 315 to 340°C, and 4.3 mass% of the residue remained. The TGA analysis results show that the residue temperature of 315 to 340°C means that it is thermally stable. Referring to Fig. 4, the glass transition temperature is shown at 0 to 30°C and a constant slope is shown up to 400°C.

[0118] Example 4-1: Method for preparing sec-butylcyclopentadienyl sodium

[0119] A reflux device and a mechanical stirrer were installed in a dried 2 L flask. 35.1 g (0.9 mol) of NaNH2 (alkali metal (B)) and 500 ml of dried diethyl ether were added to the flask and stirred using a mechanical stirrer. 100 g (0.81 mol) of sec-butylcyclopentadiene (Cp-R1 of Example 2) was slowly added dropwise to the flask. At this time, the reaction temperature did not exceed 35°C, and ammonia was confirmed through a bubbler. The mixture was reacted at room temperature for 15 hours to completion, and 104 g (0.716 mol, yield 88%) of sec-butylcyclopentadienyl sodium was obtained through filtration and distillation under reduced pressure.

[0120] Example 4-2: Method for preparing tris(sec-butylcyclopentadienyl)yttrium

[0121] A reflux device and a magnetic stirrer were installed in a dried 2 L flask. 46.7 g (0.239 mol) of YCl3(MX3) and dried diethyl ether (500 mL) were added to the flask and stirred with a stirrer. A mixture of 104 g (0.716 mol) of sec-butylcyclopentadienyl sodium dissolved in dried diethyl ether (500 mL) was slowly added dropwise to the flask. The reaction temperature did not exceed 35°C, and the reaction was completed after 15 hours. The reaction solution was filtered and distilled under reduced pressure to obtain 61 g (0.134 mol, yield 56%) of a yellow liquid compound tris(sec-butylcyclopentadienyl)yttrium.

[0122] 1 H-NMR (400 MHz, C6D6): δ 6.057~5.856 (12H, m, Cp-H), δ 2.487 (m, 3H, Cp-CH), δ 1.398 (m, 6H, Cp-C-CH2), δ 1.006 (d, 9H, C-CH3), δ 0.826 (t, 9H, Cp-CC-CH3),

[0123] Figure 5 is NMR data for tris(sec-butylcyclopentadienyl)yttrium.

[0124] Figure 6 shows TGA data for tris(sec-butylcyclopentadienyl)yttrium, and Figure 7 shows DSC data. Referring to Figure 6, under the conditions of a heating rate of 10°C / min and a sample amount of 17.290 mg, the 50% mass reduction temperature was 307 to 332°C, and 4.3 mass% of residue remained. Referring to Figure 7, a slope is shown that gradually increases from 0 to 30°C to 400°C while exhibiting a glass transition temperature.

[0125] Example 5-1: Method for preparing sec-butylcyclopentadienyl sodium

[0126] A reflux device and a mechanical stirrer were installed in a dried 2 L flask. 35.1 g (0.9 mol) of NaNH2 (alkali metal (B)) and 500 ml of dried diethyl ether were added to the flask and stirred using a mechanical stirrer. 100 g (0.81 mol) of sec-butylcyclopentadiene (Example 2 Cp-R1) was slowly added dropwise to the flask. At this time, the reaction temperature did not exceed 35°C, and ammonia was confirmed through a bubbler. The mixture was reacted at room temperature for 15 hours to completion, and 100 g (0.695 mol, yield 85%) of sec-butylcyclopentadienyl sodium was obtained through filtration and distillation under reduced pressure.

[0127] Example 5-2: Method for producing bis(sec-butylcyclopentadienyl)chloroyttrium

[0128] A reflux device and a magnetic stirrer were installed in a dried 2 L flask. 45.3 g (0.232 mol) of YCl3(MX3) and 500 mL of dried diethyl ether were added to the flask and stirred with a stirrer. A mixture of 50 g (0.348 mol) of sec-butylcyclopentadienyl sodium dissolved in 500 mL of dried diethyl ether was slowly added dropwise to the flask. At this time, the reaction temperature did not exceed 35°C and the reaction was completed after 15 hours.

[0129] The reaction solution was filtered and distilled under reduced pressure to obtain 52 g (0.141 mol, yield 61%) of crude bis(sec-butylcyclopentadienyl)chloroyttrium.

[0130] [Synthesis Formula 3]

[0131]

[0132] Example 6: Method for preparing bis(n-butylcyclopentadienyl)(N,N'-diisopropyl-ethylamidinate)yttrium

[0133] A reflux device and a magnetic stirrer were installed in a dried 250 ml flask.

[0134] Tris(n-butylcyclopentadienyl)yttrium (Example 3-2) 30 g (0.066 mol) and dried n-hexane (100 ml) were added to a flask and stirred using a magnetic stirrer. 10.4 g (0.066 mol) of N,N'-diisopropylpropionimidamide [(CH3)2CHNC(CH2CH3)NHCH(CH3)2] was slowly added dropwise to the flask and reacted at room temperature for 15 hours to complete the reaction. 20.3 g (0.044 mol, yield 67%) of bis(n-butylcyclopentadienyl)(N,N'-diisopropyl-ethylamidinate)yttrium as a yellow liquid compound was obtained through distillation under reduced pressure.

[0135] 1H-NMR (400 MHz, C6D6): δ 6.059~6.138, 6.057 (m, 8H, Cp-H), δ 3.356 (m, 2H, N-CH), δ 2.571 (m, 4H, Cp-CH2), δ 1.987 (m, 2H, NC-CH2), δ 1.624 (m, 4H, Cp-C-CH2), δ 1.376 (m, 4H, Cp-CC-CH2), δ 1.021 (d, 12H, NC-CH3), δ 0.923 (t, 6H, C-CH3), (t, 3H, NCC-CH3)

[0136] Figure 8 is NMR data for bis(n-butylcyclopentadienyl)(N,N'-diisopropyl-ethylamidinate)yttrium.

[0137] Example 7: Method for preparing bis(sec-butylcyclopentadienyl)(N,N'-diisopropyl-ethylamidinate)yttrium

[0138] A reflux device and a magnetic stirrer were installed in a dried 250 ml flask. 30 g (0.066 mol) of tris(sec-butylcyclopentadienyl)yttrium (Example 4-2) and 100 ml of dried n-hexane were added to the flask and stirred using a magnetic stirrer. 10.4 g (0.066 mol) of N,N'-diisopropylpropionimidamide [(CH3)2CHNC(CH2CH3)NHCH(CH3)2] was slowly added dropwise to the flask and reacted at room temperature for 15 hours to complete the reaction. 22.2 g (0.0484 mol, yield 73%) of the liquid compound bis(sec-butylcyclopentadienyl)(N,N'-diisopropyl-ethylamidinate)yttrium was obtained through distillation under reduced pressure.

[0139] 1H-NMR (400 MHz, C6D6): δ 6.089~6.190 (8H, m, Cp-H), δ 3.355 (m, 2H, N-CH), δ 2.789 (m, 2H, Cp-CH-C), δ 1.983 (q, 2H, NC-CH2-C), δ 1.551~1.692 (m, 4H, Cp-C-CH2-C), δ 1.284 (d, 6H, C-CH3), δ 1.027 (d, 3H, NC-CH3), δ 0.919 (t, 6H, CC-CH3), (d, 12H, NC-CH3)

[0140] Figure 9 is NMR data for bis(sec-butylcyclopentadienyl)(N,N'-diisopropyl-ethylamidinate)yttrium.

[0141] In Example 7, a novel metal precursor for forming a thin film, the 50% mass reduction temperature of the novel material is 292°C, which shows that deposition is possible at a lower temperature because it volatilizes at a temperature about 20°C lower than the average temperature.

[0142] Table 1 below shows the yield results according to the first organic solvent content (mL) based on 0.9 mol of alkali metal compound. Figure 10 is a graph for Table 1.

[0143] [Table 1]

[0144]

[0145] Referring to Table 1 and Figure 10, it is observed that the yield gradually increases from 490 to 495 mL of the first organic solvent, and the slope of the increase in yield after 495 mL sharply increases compared to before 495 mL.

[0146] Meanwhile, a phenomenon was observed where the yield decrease slope sharply decreased after 500 mL, and the yield gradually increased from 505 to 510 mL.

[0147] Therefore, the inflection point of the yield slope is around 500 mL.

[0148] Table 2 below shows the yield results according to the content (mL) of the second organic solvent based on 0.232 mol of halogen (X)-metal (M) compound. Figure 11 is a graph for Table 2.

[0149] [Table 2]

[0150]

[0151] Referring to Table 2 and Figure 11, it is observed that the yield gradually decreases at 490 to 495 mL of the second organic solvent, and the slope of the increase in yield after 495 mL sharply increases compared to before 495 mL.

[0152] Meanwhile, a phenomenon was observed where the yield decrease slope sharply decreased after 500 mL, and the yield gradually decreased from 505 to 510 mL.

[0153] Therefore, the inflection point of the yield slope is around 500 mL.

[0154] Table 3 below shows M(Cp-R1) 3-y X y This is the yield result according to the content (mL) of the third organic solvent based on 30g of the second compound indicated by . Figure 12 is a graph for Table 3.

[0155] [Table 3]

[0156]

[0157] Referring to Table 3 and Figure 12, it is observed that the yield gradually increases from 90 to 95 mL of the third organic solvent, and the slope of the increase in yield after 95 mL sharply increases compared to before 95 mL.

[0158] Meanwhile, a phenomenon was observed where the yield decrease slope sharply decreased after 100 mL, and the yield gradually increased from 105 to 110 mL.

[0159] Therefore, the inflection point of the yield slope is around 100 mL.

[0160] Although the present invention has been described with reference to the drawings exemplified above, it is to be understood that the present invention is not limited to the embodiments and drawings disclosed herein, and that various modifications may be made by those skilled in the art within the scope of the technical idea of ​​the present invention. Furthermore, even if the operational effects according to the configuration of the present invention have not been explicitly described while describing the embodiments of the present invention, it is natural that the effects predictable by the corresponding configuration should also be acknowledged.

Claims

1. (a) Cyclopentadiene (Cp) with a C4 to C6 alkyl group (R 1 )-Halogen(X) compound is added, Cp-R 1 A step of forming a first compound represented by; (b) the above Cp-R 1 After adding an alkali metal compound and a first organic solvent to the first compound represented by , a halogen (X)-metal (M) compound and a second organic solvent are added to obtain M(Cp-R 1 ) 3-y X y A step of forming a second compound represented by (y = 0 or 1); and (c) the above M(Cp-R 1 ) 3-y X y A step of preparing a metal precursor by adding a third organic solvent and a ligand to a second compound represented by ; A method for producing a metal precursor, wherein in the above halogen (X)-metal (M) compound, the metal (M) is yttrium (Y).

2. In paragraph 1, Step (a) above (a1) a step of forming a mixture by mixing purified water and an alkali metal compound; and (a2) After adding cyclopentadiene (Cp) to the above mixture, an alkyl group of C4 to C6 (R) 1 )-Halogen(X) compound and organic solvent were added, Cp-R 1 A step of forming a first compound represented by; comprising; The number of moles of purified water in step (a1) is greater than the number of moles of cyclopentadiene (Cp) in step (a2), The purified water of step (a1) above is mixed with the organic solvent of step (a2) at a weight ratio of 1:0.5 to 1.

0. In the above step (a2), cyclopentadiene (Cp): C4 to C6 alkyl group (R 1 ) - A method for producing a metal precursor by mixing a halogen (X) compound in a molar ratio of 1:0.8 to 1.

1.

3. In paragraph 1, In step (b) above, Cp-R 1 The first compound represented by: Mix the alkali metal compound in a molar ratio of 1:1.0 to 1.2, In the step (b) above, 400 to 600 mL of diethyl ether, the first organic solvent, is mixed with 0.9 mol of the alkali metal compound. A method for producing a metal precursor, wherein 400 to 600 mL of diethyl ether, a second organic solvent, is mixed with 0.232 mol of a halogen (X)-metal (M) compound in the above step (b).

4. In paragraph 1, In the step (c) above, the ligand is N,N'-diisopropylpropionimidamide [(CH 3 ) 2 CHNC(CH 2 CH 3 )NHCH(CH 3 ) 2 ] A method for producing a metal precursor comprising:

5. In paragraph 1, In the above step (c), M(Cp-R 1 ) 3-y X y A method for producing a metal precursor, comprising mixing 50 to 200 mL of normal-hexane, a third organic solvent, with 30 g of a second compound represented by .

6. In paragraph 1, The above alkali metal compounds are KOH, NaNH 2 , CH 3 Containing at least one of ONa, NaH and NaOH, A method for producing a metal precursor, wherein the above halogen (X) includes one of Cl, Br, and I.

7. In paragraph 1, The above M(Cp-R 1 ) 3-y X y A method for producing a metal precursor by mixing a second compound represented by: a ligand in a molar ratio of 1:0.5 to 1.5.

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