A precursor for thin film formation containing amidinate ligand

Abstract

The present invention relates to a thin-film forming precursor comprising a compound represented by chemical formula 1, wherein the thin-film forming precursor is liquid at room temperature and exhibits high structural stability, low viscosity, high volatility, high heat resistance, and chemical properties of being liquid at room temperature, and comprises an amidinate ligand.

Description

[Technical Field]

[0001] The present invention relates to a thin-film forming precursor containing an amidinate ligand, and more particularly to a thin-film forming precursor containing a novel amidinate ligand, which provides a low-viscosity, high-heat-resistant, highly volatile, and liquid-at-room-temperature precursor, thereby enabling the formation of high-quality thin films. [Background technology]

[0002] As the integration density increases due to the miniaturization of semiconductor element linewidths, the space available for realizing capacitor structures is limited in terms of linewidth, and existing methods for manufacturing semiconductor elements for realizing capacitor structures are reaching their limits. In particular, a problem arises in which leakage current due to the band gap deteriorates significantly when high dielectric thin films are applied. One solution to this problem is the need for a technology to form high-quality thin films, and for this purpose, it is necessary to optimize the precursors used in thin film formation.

[0003] Precursors for thin film formation consist of a central metal atom and a ligand. However, the structure of the ligand affects chemical properties such as viscosity, heat resistance, and volatility. Therefore, precursors with various ligand configurations have been developed to address these differences.

[0004] For example, prior art such as Korean Registered Patent No. 10-1660052, Korean Published Patent No. 10-2019-0109142, and 10-2021-0084297 presents a precursor containing yttrium or a lanthanum group metal, in which cyclopentadienyl and amidinate are bound as ligands. Such ligand-bound precursors are reported to be suitable for thin-film formation processes because they can improve upon the shortcomings of existing yttrium or lanthanum group metal precursors, which have low vapor pressure and high viscosity.

[0005] However, such conventional precursors may still cause various problems in the process for forming a semiconductor thin film due to their high viscosity. Therefore, it is necessary to develop a precursor that exhibits the chemical properties (such as being liquid, highly volatile, and highly heat-resistant) required in the semiconductor thin film forming process while improving the viscosity property. In particular, referring to the results of the prior art, a chemical structure containing an amidinate as a ligand is expected to be able to obtain the chemical properties of the precursor required in the thin film forming process.

Summary of the Invention

Problems to be Solved by the Invention

[0006] The present invention has been devised in consideration of the above-described prior art, and an object thereof is to provide a precursor for thin film formation containing a novel amidinate ligand.

[0007] Another object is to provide a precursor for thin film formation that exhibits chemical properties of low viscosity, high heat resistance, and high volatility by containing the ligand.

Means for Solving the Problems

[0008] The precursor for thin film formation of the present invention for achieving the above object contains a compound represented by the following Chemical Formula 1 and is characterized by being liquid at room temperature. [Chemical Formula 1] (L) n -M-(AMD) m

[0009] In the above Chemical Formula 1, AMD is an amidinate ligand, M is a central metal atom, which can be any one of the Group 2 to Group 6 elements, Group 13 element, Group 15 element, transition metal and rare earth element, L is a ligand the same as or different from the above AMD, and when it is different from the above AMD, it is a substituted or unsubstituted cyclopentadienyl group, amine, alcohol, alkyl, aryl, aminoamine, alkoxyamine, aminoalcohol, alkoxyalcohol, imide, diamine, dialcohol, formidinate, guanidinate, beta-diketonate, ketoimine, amide and halide, n is an integer from 0 to 5, and m is an integer from 1 to 6.

[0010] At this time, the above AMD may be a ligand represented by the following Chemical Formula 2. [Chemical Formula 2] [Chem.]

[0011] In the above Chemical Formula 2, R1 and R3 are each independently a linear, branched or cyclic alkyl group or alkenyl group having 1 to 5 carbon atoms, and R2 is a hydrogen atom or a linear, branched or cyclic alkyl group or alkenyl group having 1 to 5 carbon atoms.

[0012] Also, in the above Chemical Formula 2, the above R2 may be a linear, branched or cyclic alkyl group or alkenyl group having 2 to 5 carbon atoms.

[0013] Also, in the above Chemical Formula 2, the above R1 and R3 are each independently a linear, branched or cyclic alkyl group or alkenyl group having 2 to 5 carbon atoms, and the above R2 may be a linear, branched or cyclic alkyl group or alkenyl group having 2 to 5 carbon atoms.

[0014] Also, in the above Chemical Formula 2, the above R1 and R3 may be methyl groups.

[0015] Also, in the above Chemical Formula 2, the above R2 may be an isopropyl group.

[0016] Furthermore, in the above chemical formula 2, R1 and R3 may each independently be a linear alkyl group or alkenyl group of C1 to C5.

[0017] Furthermore, in the chemical formula 2, R1 and R3 are each independently a linear alkyl group or alkenyl group of C1 to C5, and R2 may also be a linear alkyl group or alkenyl group of C1 to C5.

[0018] Furthermore, in the above chemical formula 2, R1 and R3 are all the same and may be linear, branched, or cyclic alkyl or alkenyl groups of C1 to C5.

[0019] Furthermore, in the above chemical formula 2, R1 to R3 are all the same and may be linear, branched, or cyclic alkyl or alkenyl groups of C1 to C4.

[0020] Furthermore, the thin-film formation precursor is preferably a low-viscosity precursor with a viscosity of 60 cP (25°C) or less. [Effects of the Invention]

[0021] The thin-film formation precursor according to the present invention can be made to exhibit high structural stability, low viscosity, high volatility, high heat resistance, and chemical properties of a liquid form at room temperature by containing an amidinate ligand.

[0022] Therefore, the thin-film formation precursor containing the amidinate ligand exhibits physical properties suitable for use in the thin-film formation process, enabling the formation of a high-quality thin film without thermal decomposition or residual issues in the piping due to high viscosity during the process, and providing a semiconductor device containing a thin film manufactured by the thin-film formation method. [Brief explanation of the drawing]

[0023] [Figure 1] This is the 1H-NMR analysis result of diethyl-ethylamidinate ligand. [Figure 2] This is the TGA analysis result for diethyl-ethylamidinate ligand. [Figure 3] This is the 1H-NMR analysis result of diethyl-n-propylamidinate ligand. [Figure 4] This is the TGA analysis result for diethyl-n-propylamidinate ligand. [Figure 5] This is the result of the 1H-NMR analysis of dinormalpropyl-ethylamidinate ligand. [Figure 6] This is the TGA analysis result for dinormalpropyl-ethylamidinate ligand. [Figure 7] This is the 1H-NMR analysis result for bis(ethylcyclopentadienyl)(diethyl-ethylamidinate)yttrium. [Figure 8] This is the TGA analysis result for bis(ethylcyclopentadienyl)(diethyl-ethylamidinate)yttrium. [Figure 9] This is the DSC analysis result for bis(ethylcyclopentadienyl)(diethyl-ethylamidinate)yttrium. [Figure 10] This is the 1H-NMR analysis result for bis(ethylcyclopentadienyl)(diethyl-n-propylamidinate)yttrium. [Figure 11] This is the TGA analysis result for bis(ethylcyclopentadienyl)(diethyl-n-propylamidinate)yttrium. [Figure 12] This is the 1H-NMR analysis result for bis(isopropylcyclopentadienyl)(diethyl-ethylamidinate)yttrium. [Figure 13] This is the 1H-NMR analysis result for bis(methylcyclopentadienyl)(diethyl-n-propylamidinate)yttrium. [Figure 14] This is the TGA analysis result for bis(methylcyclopentadienyl)(diethyl-n-propylamidinate)yttrium. [Figure 15]This is the 1H-NMR analysis result for bis(methylcyclopentadienyl)(dinorpropyl-ethylamidinate)yttrium. [Figure 16] This is the TGA analysis result for bis(methylcyclopentadienyl)(dinorpropyl-ethylamidinate)yttrium. [Figure 17] This is the 1H-NMR analysis result for bis(ethylcyclopentadienyl)(dimethyl-propylamidinate)yttrium. [Figure 18] This is the TGA analysis result for bis(ethylcyclopentadienyl)(dimethyl-propylamidinate)yttrium. [Figure 19] This is the DSC analysis result for bis(ethylcyclopentadienyl)(dimethylpropylamidinate)yttrium. [Figure 20] This is the 1H-NMR analysis result of bis(ethylcyclopentadienyl)(diethyl-n-propylamidinate)scandium. [Figure 21] This is the TGA analysis result for bis(ethylcyclopentadienyl)(diethyl-n-propylamidinate)scandium. [Figure 22] This is the TGA analysis result for bis(isopropylcyclopentadienyl)(diethyl-n-propylamidinate)cerium. [Figure 23] This is the DSC analysis result for bis(isopropylcyclopentadienyl)(diethyl-n-propylamidinate)cerium. [Figure 24] This is the TGA analysis result for bis(ethylcyclopentadienyl)(diethyl-ethylamidinate)gadolinium. [Figure 25] This is the DSC analysis result for bis(ethylcyclopentadienyl)(diethyl-ethylamidinate)gadolinium. [Figure 26] This is the TGA analysis result for bis(ethylcyclopentadienyl)(diethyl-ethylamidinate)dysprosium. [Figure 27]This is the DSC analysis result for bis(ethylcyclopentadienyl)(diethyl-ethylamidinate)dysprosium. [Figure 28] This is the 1H-NMR analysis result of bis(ethylcyclopentadienyl)(diethyl-ethylamidinate)lutetium. [Figure 29] This is the TGA analysis result for bis(ethylcyclopentadienyl)(diethyl-ethylamidinate)lutetium. [Figure 30] This is the DSC analysis result for bis(ethylcyclopentadienyl)(diethyl-ethylamidinate)lutetium. [Figure 31] This is the 1H-NMR analysis result for tris(diethyl-n-propylamidinate)yttrium. [Figure 32] This is the TGA analysis result for tris(diethyl-n-propylamidinate)yttrium. [Figure 33] This is the TGA analysis result for tris-(diethyl-n-propylamidinate)terbium. [Figure 34] This is the DSC analysis result for tris-(diethyl-n-propylamidinate)terbium. [Figure 35] This is the TGA analysis result for tris-(diethyl-n-propylamidinate)dysprosium. [Figure 36] This is the DSC analysis result for tris-(diethyl-n-propylamidinate)dysprosium. [Figure 37] This is the TGA analysis result for tris-(diethyl-n-propylamidinate)erbium. [Figure 38] This is the DSC analysis result for tris-(diethyl-n-propylamidinate)erbium. [Figure 39] This is the TGA analysis result for tris-(diethyl-n-propylamidinate)ytterbium. [Figure 40] This is the 1H-NMR analysis result of tris-(diethyl-n-propylamidinate)lutetium. [Figure 41]This is the TGA analysis result for tris-(diethyl-n-propylamidinate)lutetium. [Figure 42] This is the DSC analysis result for tris-(diethyl-n-propylamidinate)lutetium. [Figure 43] This is the 1H-NMR analysis result for (CH2CH2CH2N-C(CH2CH3)=N-CH2CH2CH3)2Hf(DMA)2. [Figure 44] These are the TGA(a) and DSC(b) analysis results for (CH2CH2CH2N-C(CH2CH3)=N-CH2CH2CH3)2Hf(DMA)2. [Figure 45] This is the 1H-NMR analysis result for (CH2CH2N-C(CH2CH2CH3)=N-CH2CH3)2Hf(DMA)2. [Figure 46] These are the TGA(a) and DSC(b) analysis results for (CH2CH2N-C(CH2CH2CH3)=N-CH2CH3)2Hf(DMA)2. [Figure 47] This is the 1H-NMR analysis result for (CH2CH2N-C(CH2CH2CH3)=N-CH2CH3)2Hf(EMA)2. [Figure 48] These are the TGA(a) and DSC(b) analysis results for (CH2CH2N-C(CH2CH2CH3)=N-CH2CH3)2Hf(EMA)2. [Figure 49] This is the 1H-NMR analysis result for (CH2CH2N-C(CH2CH2CH3)=N-CH2CH3)2Zr(DMA)2. [Figure 50] These are the TGA(a) and DSC(b) analysis results for (CH2CH2N-C(CH2CH2CH3)=N-CH2CH3)2Zr(DMA)2. [Figure 51] This is the 1H NMR analysis result of (2-ethyl-N,N-diethylamidinate)bis(dimethylamino)borane. [Figure 52] This is the result of the 11B NMR analysis of (2-ethyl-N,N-diethylamidinate)bis(dimethylamino)borane. [Figure 53]This is the 1H NMR analysis result of (2-methyl-N,N-diisopropylamidinate)bis(dimethylamino)borane. [Figure 54] This is the result of the 11B NMR analysis of (2-methyl-N,N-diisopropylamidinate)bis(dimethylamino)borane. [Figure 55] This is the 1H NMR analysis result of (2-ethyl-N,N-diethylamidinate)(N,N-dimethylethylenediamino)borane. [Figure 56] This is the result of 11B NMR analysis of (2-ethyl-N,N-diethylamidinate)(N,N-dimethylethylenediamino)borane. [Figure 57] This is the 1H NMR analysis result of (N-ethyl-2-isobutyl-N-propylamidinate)bis(dimethylamino)borane. [Figure 58] This is the result of the 11B NMR analysis of (N-ethyl-2-isobutyl-N-propylamidinate)bis(dimethylamino)borane. [Modes for carrying out the invention]

[0024] The present invention will now be described in more detail. The terms and words used herein and in the claims shall not be construed to be limited to their ordinary or dictionary meanings, but shall be interpreted in a sense and concept consistent with the technical idea of ​​the present invention, in accordance with the principle that inventors may appropriately define the concepts of terms in order to best describe their invention. The thin-film formation precursor according to the present invention contains a compound represented by the following chemical formula 1 and is characterized by being liquid at room temperature. [Chemical formula 1] (L) n -M-(AMD) m

[0025] In the above chemical formula 1, AMD is an amidinate ligand, M is a central metal atom from any of the Group 2 to 6 elements, Group 13 elements, Group 15 elements, transition metals, and rare earth elements, L is a ligand that is the same as or different from AMD, and if it is different from AMD, it is any of the substituted or unsubstituted cyclopentadienyl group, amine, alcohol, alkyl, aryl, aminoamine, alkoxyamine, amino alcohol, alkoxy alcohol, imide, diamine, dialcohol, formidinate, guanidinate, beta-diketonate, ketoiminate, amide, and halide, n is an integer from 0 to 5, and m is an integer from 1 to 6.

[0026] Furthermore, the AMD can be a ligand compound represented by the following chemical formula 2. [Chemical formula 2] [ka]

[0027] In the above chemical formula 2, R1 and R3 are each independently a linear, branched, or cyclic alkyl or alkenyl group of C1 to C5, and R2 is a hydrogen atom or a linear, branched, or cyclic alkyl or alkenyl group of C1 to C5.

[0028] The amidinate ligand is used as a ligand for the thin-film formation precursor compound of the present invention. In particular, R1 and R3 may be the same or different in the amidinate ligand, but it may be configured in various forms depending on the desired effect of the precursor containing the ligand.

[0029] Furthermore, in the above chemical formula 2, R2 may be a hydrogen atom or a linear, branched, or cyclic alkyl or alkenyl group of C1 to C5, but as a non-limiting example, R2 may include n-alkyl groups such as an ethyl group, a propyl group, or a butyl group.

[0030] The precursor containing the amidinate ligand represented by chemical formula 2 exhibits low viscosity, high thermal stability and volatility, and can exist in a liquid state at room temperature. Therefore, it was found that the chemical properties of the target precursor can be obtained through the synthesis of the ligand-containing precursor. In other words, it exhibits improved physical properties overall compared to various precursor compounds containing amidinate ligands in the conventional art, thus providing improved effects as a precursor and in the thin-film formation process using the precursor.

[0031] The amidinate ligand represented by the chemical formula 2 can take on various forms with attached functional groups.

[0032] In one embodiment, R2 may be a linear, branched, or cyclic alkyl or alkenyl group of C2 to C5. When R2 is provided as C2 or greater, structural asymmetry is increased while minimizing intramolecular structural steric hindrance compared to when it is H or C1, thereby reducing intermolecular interference. Therefore, the precursor containing the ligand is not only easy to form into a liquid state, but also exhibits low viscosity properties.

[0033] On the other hand, R1 and R3 may each be independently a linear, branched, or cyclic alkyl or alkenyl group of C2 to C5, and R2 may be a linear, branched, or cyclic alkyl or alkenyl group of C2 to C5.

[0034] In another embodiment, R1 and R3 may be methyl groups, and R2 may be an isopropyl group.

[0035] Furthermore, R1 and R3 may each be independently a linear alkyl group or alkenyl group of C1 to C5.

[0036] Linear alkyl or alkenyl groups, compared to branched or cyclic groups, can improve volatility and vapor pressure by reducing molecular weight through minimizing the ligand structure. Therefore, in one embodiment of the present invention, each of R1 and R3 can be composed of a linear alkyl or alkenyl group. In this case, the vapor pressure of the thin-film formation precursor containing the ligand is improved, which may lead to improvements such as ease of processing during the thin-film formation process using the precursor.

[0037] In addition to the vapor pressure improvement effect, the ligand, in which R1 and R3 are each composed of linear alkyl groups, has a high degree of structural freedom, and therefore can provide an effect of improving the degree of freedom of the precursor to which the ligand is applied. This effect minimizes interference between precursors, thereby creating the liquefaction and low viscosity properties of the precursor.

[0038] Therefore, in one embodiment, the amidinate ligand can be composed of linear alkyl or alkenyl groups in the chemical formula 2, in which case the precursor containing the ligand can have an improved vapor pressure, making it easier to form in liquid form through improved degrees of freedom, and also obtaining low viscosity properties.

[0039] On the other hand, R1 and R3 may each be independently a linear alkyl group or alkenyl group of C1 to C5, and R2 may also be a linear alkyl group or alkenyl group of C1 to C5.

[0040] Furthermore, R1 and R3 are all the same and may be linear, branched, or cyclic alkyl or alkenyl groups of C1 to C5.

[0041] Furthermore, R1 to R3 are all the same and may be linear, branched, or cyclic alkyl or alkenyl groups of C1 to C4.

[0042] Exemplary structures of such amidinate ligands include one or more selected from the following chemical structures. [ka] JPEG2026520762000005.jpg206155JPEG2026520762000006.jpg86150

[0043] On the other hand, the thin-film formation precursor containing the amidinate ligand may have a central metal atom that is one of the following: group 2 to 6 elements, group 13 elements, group 15 elements, transition metals, or rare earth elements.

[0044] As a non-limiting example, the central metal atom may be any of yttrium (Y), scandium (Sc), or a lanthanum group element.

[0045] Furthermore, as a non-limiting example, the thin-film formation precursor represented by chemical formula 1 includes compounds represented by the following diverse chemical structures.

[0046] For example, the following compounds can be cited as examples of compounds containing a substituted or unsubstituted cyclopentadienyl group L. [ka] JPEG2026520762000008.jpg186170JPEG2026520762000009.jpg187170JPEG2026520762000010.jpg186170

[0047] Furthermore, if L is the same as AMD, the following compounds can be given as examples. [ka] JPEG2026520762000012.jpg220150

[0048] Furthermore, when L is an amine group, the following compounds can be given as examples. [ka] JPEG2026520762000014.jpg121146JPEG2026520762000015.jpg126149JPEG2026520762000016.j pg123149JPEG2026520762000017.jpg105152JPEG2026520762000018.jpg106151JPEG20265207620 00019.jpg106150JPEG2026520762000020.jpg108152JPEG2026520762000021.jpg105149JPEG202 6520762000022.jpg107153JPEG2026520762000023.jpg107151JPEG2026520762000024.jpg106151

[0049] The thin-film formation precursor according to the present invention, by containing an amidinate ligand, can be provided in a low-viscosity, high-heat-resistant, highly volatile, and liquid form at room temperature, thereby enabling the formation of high-quality thin films. In particular, the thin-film formation precursor has a viscosity of 60 cP (25°C) or less and can exhibit physical properties suitable for the thin-film formation process.

[0050] Furthermore, the thin-film formation precursor of the present invention may further contain a solvent for dissolving or diluting the precursor compound, taking into consideration the conditions and efficiency of the thin-film formation process. The solvent may be C1-C 16 You can use any of the saturated or unsaturated hydrocarbons, ketones, ethers, glycyles, esters, tetrahydrofurans, tertiary amines, or mixtures thereof. 16 Examples of saturated or unsaturated hydrocarbons include pentane, cyclohexane, ethylcyclohexane, heptane, octane, and toluene, while examples of tertiary amines include dimethylethylamine and triethylamine.

[0051] In particular, depending on the chemical structure, the compound of the thin-film formation precursor may be in a solid state at room temperature, but in this case, the compound can be dissolved by including the solvent. That is, when the solvent is included, it is included in a solvent and quantity that is capable of dissolving the precursor compound, and it is preferable that it is included in an amount of 1 to 99% by weight relative to the total weight of the thin-film formation precursor.

[0052] Since the precursor containing or not containing the aforementioned solvent can be vaporized, it can be supplied into the chamber as a precursor gas. Therefore, if the precursor compound exists in liquid form at room temperature and can be easily vaporized, the thin film formation process can be carried out without a separate solvent.

[0053] In this case, the thin film formation process can be carried out by any of the following: a spin-on dielectric (SOD) process, a low-temperature plasma (LTP) process, a chemical vapor deposition (CVD) process, a plasma-enhanced chemical vapor deposition (PECVD) process, a high-density plasma-chemical vapor deposition (HDPCVD) process, an atomic layer deposition (ALD) process, or a plasma-enhanced atomic layer deposition (PEALD) process.

[0054] For example, when applying the HDP-CVD process, it can be carried out under higher vacuum and higher power compared to atmospheric pressure chemical vapor deposition (AP-CVD), low-pressure chemical vapor deposition (LP-CVD), or plasma-enhanced chemical vapor deposition (PE-CVD), thus enabling the formation of thin films that are structurally dense and possess excellent mechanical properties.

[0055] For this purpose, the thin film formation method according to the present invention includes the step of forming a thin film on a substrate using the thin film formation precursor.

[0056] Specifically, the step of forming a thin film on the substrate may include the step of depositing the thin film formation precursor onto the surface of the substrate to form a precursor thin film, and the step of reacting the precursor thin film with a reactant.

[0057] Furthermore, the procedure may include vaporizing the thin-film forming precursor and transferring it into the chamber for deposition of the precursor.

[0058] Furthermore, the step of forming a thin film on the substrate may include a step of supplying the thin-film formation precursor to the substrate and applying plasma in the presence of reactants to form a thin film of metal, oxide, nitride, oxynitride, etc.

[0059] The process of forming the thin film can be carried out under chamber pressure conditions of 0.1 to 1000 mTorr. The source power for forming the plasma in the chamber should be 500 to 9,000 W, and the bias power should be 0 to 5,000 W. The bias power may be omitted depending on the circumstances.

[0060] Furthermore, the process of forming a thin film on the substrate is preferably carried out in a temperature range of 150 to 500°C.

[0061] Furthermore, when supplying the thin-film formation precursor, a second metal precursor may be introduced as needed to further improve the electrical properties of the final metal film, i.e., capacitance or leakage current value. The second metal precursor may also be selectively supplied, containing one or more metals (M'') selected from magnesium (Mg), strontium (Sr), barium (Ba), lanthanum (Ln), titanium (Ti), zirconium (Zr), hafnium (Hf), niobium (Nb), tantalum (Ta), aluminum (Al), indium (In), silicon (Si), germanium (Ge), and tin (Sn) atoms. The second metal precursor may be an alkylamide compound or alkoxy compound containing the metal. For example, if the metal is Si, then SiH(N(CH3)2)3, SiH2(N(C2H5)2)2, SiH2(NHtBu)2, SiH3(N(iPr)2), Si(OC4H9)4, Si(OC2H5)4, Si(OCH3)4, Si(OC(CH3)3)4, etc. can be used as the second metal precursor.

[0062] The supply of the second metal precursor can be carried out in the same manner as the supply method for the thin film formation precursor, and the second metal precursor may be supplied onto the thin film formation substrate together with the precursor, or it may be supplied sequentially after the supply of the precursor is completed.

[0063] The precursors described above and the selectively selected second metal precursor are preferably kept at a temperature of 50 to 250°C, and more preferably at a temperature of 100 to 200°C, until they are supplied into the reaction chamber for contact with the thin film forming substrate.

[0064] Furthermore, after the precursor supply step and prior to the supply of the reactants, a step can be performed to purge the reactor with an inert gas such as argon (Ar), nitrogen (N2), or helium (He) in order to assist the movement of the precursor and selectively the second metal precursor onto the substrate, to ensure that the reactor has a pressure suitable for deposition, and to release impurities present in the chamber to the outside. At this time, it is preferable that the purging of the inert gas is performed so that the pressure inside the reactor is 1 to 5 Torr.

[0065] Furthermore, any of the following or a mixture thereof can be used as the reactant: nitrogen (N2), ammonia (NH3), hydrazine (N2H4), nitrous oxide (N2O), oxygen (O2), water vapor (H2O), ozone (O3), hydrogen peroxide (H2O2), silane, hydrogen (H), and diborane (B2H6). When carried out in the presence of an oxidizing gas such as water vapor, oxygen, or ozone, a magnesium oxide thin film can be formed, and when carried out in the presence of a reducing gas such as hydrogen, ammonia, hydrazine, or silane, a thin film of elemental metal or metal nitride can be formed. In addition, a metal oxynitride thin film can also be formed by mixing the reactants.

[0066] In addition to plasma treatment, heat treatment or light irradiation treatment steps can also be performed, but these are for providing thermal energy for the deposition of the thin film precursor and can be carried out by conventional methods. Preferably, in order to produce a thin film having the desired physical state and composition at a sufficient growth rate, it is preferable to perform the treatment steps so that the temperature of the substrate in the reactor is 100 to 1,000°C, preferably 250 to 400°C.

[0067] Furthermore, during the aforementioned processing steps, a step may be performed to purge the reactor with an inert gas such as argon (Ar), nitrogen (N2), or helium (He) in order to assist the movement of the reactants onto the substrate, to ensure that the reactor has a pressure suitable for deposition, and to release impurities or by-products present in the reactor to the outside.

[0068] The above-described process of adding the thin-film formation precursor, adding the reactants, and adding the inert gas constitutes one cycle, and a thin film can be formed by repeating this process one or more times.

[0069] Furthermore, by applying the thin-film formation process, a variety of semiconductor devices including thin films can be manufactured.

[0070] The effects of the present invention will be explained below with reference to examples. Example 1: Synthesis of diethyl ethyl amidinate (Et2Et-AMD) 132.1 g (0.75 mol) of triethyl ortho-propionate and 74.3 g (1.65 mol) of ethylamine were placed in a 500 ml Schlenk flask, and the mixture was cooled to -30°C and stirred. At the same temperature, 99.0 g (1.65 mol) of acetic acid was slowly added dropwise, and the mixture was refluxed at 170°C. After 18 hours, the solvent was removed under reduced pressure, and the mixture was extracted with 5N sodium hydroxide (NaOH) aqueous solution and diethyl ether. After drying over magnesium sulfate, the mixture was filtered, and the solvent was removed under reduced pressure. Distillation under reduced pressure yielded 46.1 g (48%) of a colorless liquid compound. The NMR analysis results are shown in Figure 1. 1 H NMR (CDCl3, 25℃): 1.13(m, 9H), 2.20(q, 2H), 3.17(m, 4H) Purification conditions: 75~78℃@2.4torr

[0071] The pale yellow liquid was found to be 0% during TGA analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass. This result was confirmed by the TGA analysis results (Figure 2), which represent the percentage of weight loss due to temperature change.

[0072] Example 2: Synthesis of diethyl-n-propylamidinate (Et2nPr-AMD) 122.5 g (0.64 mol) of 1,1,1-triethoxybutane and 58.0 g (1.29 mol) of ethylamine were placed in a 500 ml Schlenk flask, and the mixture was cooled to -30°C and stirred. At the same temperature, 77.3 g (1.29 mol) of acetic acid was slowly added dropwise, and the mixture was refluxed at 170°C. After 18 hours, the solvent was removed under reduced pressure, and the mixture was extracted with 5N sodium hydroxide (NaOH) aqueous solution and diethyl ether. After drying over magnesium sulfate, the mixture was filtered, and the solvent was removed under reduced pressure. Distillation under reduced pressure yielded 36.6 g (40%) of a colorless liquid compound. The NMR analysis results are shown in Figure 3. 1 H NMR (CDCl3, 25℃): 0.98(t, 3H), 1.15(m, 6H), 1.59(m, 2H), 2.15(m, 2H), 3.22(m, 4H) Purification conditions: 82~87℃@0.5torr

[0073] The pale yellow liquid was found to be 0% during TGA analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass. This result was confirmed by the TGA analysis results (Figure 4), which represent the percentage of weight loss due to temperature change.

[0074] Example 3: Synthesis of dinormalpropyl-ethylamidinate (nPr2Et-AMD) 132.1 g (0.75 mol) of triethyl ortho-propionate and 97.5 g (1.65 mol) of n-Propylamine were placed in a 500 ml Schlenk flask, cooled to -30 °C and stirred. 49.5 g (0.83 mol) of acetic acid was slowly added dropwise at the same temperature, and the mixture was refluxed at 170 °C. After 18 hours, the solvent was removed under reduced pressure, and the residue was extracted with 5N aqueous sodium hydroxide (NaOH) solution and diethyl ether. After drying with magnesium sulfate, it was filtered and the solvent was removed under reduced pressure. Distillation under reduced pressure gave 48.0 g (41%) of a colorless liquid compound. The NMR analysis results are as shown in Figure 5. 1 H NMR (CDCl3, 25 °C): 0.70 (t, 6H), 0.89 (t, 3H), 1.31 (m, 4H), 1.97 (m, 2H), 2.90 (m, 4H) Purification conditions: 80 - 90 °C @ 0.5 torr

[0075] The pale yellow liquid was 0% during TGA analysis measured at a heating rate of 10 °C / min in an atmosphere where nitrogen was flowing at 200 ml / min, leaving almost no residual mass. Such results were confirmed by the TGA analysis results (Figure 6) representing the percentage of weight loss due to thermal chlorination.

[0076] Example 4: Synthesis of Bis(ethylcyclopentadienyl)(diethyl-ethylamidinato)yttrium [(EtCp)2Y(Et2Et-AMD)] 32.83 g (0.256 mol) of diethyl-ethylamidinate was charged into 300 ml of THF, cooled to -78 °C, and then 102.4 ml (0.256 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise to prepare Li-(Et2Et-AMD). The solution was stirred at -78 °C for 30 minutes, then warmed to room temperature and stirred further at room temperature for 2 hours. The prepared Li-(Et2Et-AMD) solution was slowly added dropwise at room temperature to a flask containing (EtCp)2YCl and stirred at room temperature for 12 hours. The mixture was evaporated under vacuum, dissolved in 250 ml of pentane, filtered, and the solvent and volatiles were evaporated under vacuum. A pale yellow liquid was obtained from the resulting red liquid at 165 °C and 40 mTorr. The yield was 60.1 g (58.3%). The NMR analysis results are shown in Figure 7. 1 H NMR(C6D6, 25℃): 0.85(t, 3H), 0.98(t, 6H), 1.20(t, 6H), 1.97(q, 2H), 2.48(q, 4H), 2.97(q, 4H), 6.0(dt, 8H)

[0077] The pale yellow liquid was found to be 0% during TGA analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass. This result was confirmed by the TGA analysis results (Figure 8), which represent the percentage of weight loss due to thermal chlorination.

[0078] A pale yellow liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes. During DSC analysis, measured at a heating rate of 10°C / min, a decomposition peak was observed at 377°C. This result was confirmed by the DSC analysis results (Figure 9), which represent the change in thermal energy due to thermal chlorination.

[0079] A pale yellow liquid sample was placed in a rotary viscometer, and its viscosity was measured using a low-viscosity spindle at 25°C. A viscosity of 30 cP was measured while measuring viscosity at 12 RPM.

[0080] Example 5: Synthesis of bis(ethylcyclopentadienyl)(diethyl-n-propylamidinate)yttrium [(EtCp)2Y(Et2nPr-AMD)] 36.43 g (0.256 mol) of diethyl-n-propylamidinate was charged into 300 ml of THF, cooled to -78°C, and then 102.4 ml (0.256 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise to prepare Li-(Et2nPr-AMD). The solution was stirred at -78°C for 30 minutes, then warmed to room temperature and stirred further at room temperature for 2 hours. The prepared Li-(Et2nPr-AMD) solution was slowly added dropwise at room temperature to a flask containing Y(EtCp)2Cl and stirred at room temperature for 12 hours. The mixture was evaporated under vacuum, dissolved in 250 ml of pentane, filtered, and the solvent and volatiles were evaporated under vacuum. The resulting red liquid was distilled at 185°C and 40 mTorr to obtain a pale yellow liquid. The yield was 65.1 g (61.0%). The NMR analysis results are shown in Figure 10. 1 H NMR(C6D6, 25℃): 0.83(t, 3H), 0.99(t, 6H), 1.20(t, 6H), 1.36(q, 2H), 1.98(q, 2H), 2.50(q, 4H), 3.00(q, 4H), 6.0(dt, 8H)

[0081] The pale yellow liquid was found to be 0% during TGA analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass. This result was confirmed by the TGA analysis results (Figure 11), which represent the percentage of weight loss due to temperature change.

[0082] A pale yellow liquid sample was placed in a rotary viscometer, and its viscosity was measured using a low-viscosity spindle at 25°C. A viscosity of 28 cP was measured while measuring viscosity at 20 RPM.

[0083] Example 6: Synthesis of bis(isopropylcyclopentadienyl)(diethyl-ethylamidinate)yttrium [(iPrCp)2Y(Et2Et-AMD)] 32.83 g (0.256 mol) of diethyl-ethylamidinate was charged into 300 ml of THF, cooled to -78 °C, and then 102.4 ml (0.256 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise to prepare Li-(Et2Et-AMD). The solution was stirred at -78 °C for 30 minutes, then warmed to room temperature and stirred further at room temperature for 2 hours. The prepared Li-(Et2Et-AMD) solution was slowly added dropwise at room temperature to a flask containing (iPr)2YCl and stirred at room temperature for 12 hours. The mixture was evaporated under vacuum, dissolved in 250 ml of pentane, filtered, and the solvent and volatiles were evaporated under vacuum. The resulting red liquid was distilled at 170 °C and 20 m Torr to obtain a yellow liquid. The yield was 63.6 g (70.1%). 1 The results of the 1H NMR (Bruker AV400MHz HD) analysis are shown in Figure 12. 1 H NMR(C6D6, 25℃): 0.85(t, 3H), 1.02(t, 6H), 1.24(d, 12H), 1.94(q, 2H), 2.82(m, 2H), 3.01(q, 4H), 6.01(dt, 8H)

[0084] The pale yellow liquid was found to be 0% during TGA (SDT Q600, TA Instruments) analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass.

[0085] Example 7: Synthesis of bis(methylcyclopentadienyl)(diethyl-n-propylamidinate)yttrium [(MeCp)2Y(Et2nPr-AMD)] 36.43 g (0.256 mol) of diethyl-n-propylamidinate was charged into 300 ml of THF, cooled to -78°C, and then 102.4 ml (0.256 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise to prepare Li-(Et2nPr-AMD). The solution was stirred at -78°C for 30 minutes, then warmed to room temperature and stirred further at room temperature for 2 hours. The prepared Li-(Et2nPr-AMD) solution was slowly added dropwise at room temperature to a flask containing (MeCp)2YCl and stirred at room temperature for 12 hours. The mixture was evaporated under vacuum, dissolved in 250 ml of pentane, filtered, and the solvent and volatiles were evaporated under vacuum. A colorless liquid was obtained from the resulting red liquid at 170°C and 67 mTorr. The yield was 59.11 g (59.4%). 1 The results of the 1H NMR (Bruker AV400MHz HD) analysis are shown in Figure 13. 1 H NMR (C6D6, 25℃): 0.83(t, 3H), 0.98(t, 6H), 1.34(t, 2H), 1.96(q,2H), 2.11(s, 6H), 2.97(q, 4H), 6.0(dt, 8H)

[0086] The colorless liquid was found to be 0.9% during TGA (SDT Q600, TA Instruments) analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass. These results are shown in Figure 14, which represents the percentage of weight loss due to temperature change in the TGA analysis.

[0087] A colorless liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes. During DSC analysis (Discovery 25, TA Instruments) performed at a heating rate of 10°C / min, a decomposition peak was observed at 410°C.

[0088] Example 8: Synthesis of bis(methylcyclopentadienyl)(dinorpropyl-ethylamidinate)yttrium [(MeCp)2Y(nPr2Et-AMD)] 40.02 g (0.256 mol) of dinormalpropyl ethyl amidinate was charged into 300 ml of THF, cooled to -78°C, and then 102.4 ml (0.256 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise to prepare Li-(nPr2Et-AMD). The solution was stirred at -78°C for 30 minutes, then warmed to room temperature and stirred further at room temperature for 2 hours. The prepared Li-(nPr2Et-AMD) solution was slowly added dropwise at room temperature to a flask containing (MeCp)2YCl and stirred at room temperature for 12 hours. The mixture was evaporated under vacuum, dissolved in 250 ml of pentane, filtered, and the solvent and volatiles were evaporated under vacuum. A yellow liquid was obtained from the resulting red liquid at 155°C and 113 mTorr. The yield was 60.1 g (58.3%). The NMR (Bruker AV400MHz HD) analysis results are shown in Figure 15. 1 H NMR (C6D6, 25℃): 0.87(t, 9H), 1.37(q, 4H), 2.01(q, 2H), 2.12(s,6H), 2.96(q, 4H), 6.0(dt, 8H)

[0089] The yellow liquid was present at 1.6% during TGA (SDT Q600, TA Instruments) analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass. This result is shown in Figure 16, which represents the percentage of weight loss due to temperature change in the TGA analysis.

[0090] Example 9: Synthesis of bis(ethylcyclopentadienyl)(dimethylpropylamidinate)yttrium [(Et(Cp)2Y(Me2-nPrAMD)] 29.24 g (0.256 mol) of dimethyl-n-propylamidinate was charged into 300 ml of THF, cooled to -78°C, and then 102.4 ml (0.256 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise to prepare Li-(Me2-nPrAMD). The solution was stirred at -78°C for 30 minutes, then warmed to room temperature and stirred further at room temperature for 2 hours. The prepared Li-(Me2-nPrAMD) solution was slowly added dropwise at room temperature to a flask containing (EtCp)2YCl and stirred at room temperature for 12 hours. The mixture was evaporated under vacuum, dissolved in 250 ml of pentane, filtered, and the solvent and volatiles were evaporated under vacuum. An orange liquid was obtained from the resulting pale pink liquid at 152°C and 44 mTorr. The yield was 85.0 g (85.5%). 1 The results of the 1H NMR (Bruker AV400MHz HD) analysis are shown in Figure 17. 1 H NMR (C6D6, 25℃): 0.85(t, 3H), 1.16(t, 6H), 1.33(m, 2H), 2.00(m, 2H), 2.45(q, 4H), 2.69(s, 6H), 6.0(dt, 8H)

[0091] The orange liquid was present at 1% during TGA (SDT Q600, TA Instruments) analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass. This result is shown in Figure 18, which represents the percentage of weight loss due to temperature change in the TGA analysis.

[0092] A pale yellow liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes. During DSC analysis (Discovery 25, TA Instruments) performed at a heating rate of 10°C / min, a decomposition peak was observed at 422°C. This result is shown in Figure 19, which represents the change in thermal energy due to temperature change in the DSC analysis.

[0093] Example 10: Synthesis of bis(ethylcyclopentadienyl)(diethyl-n-propylamidinate)scandium [(EtCp)2Sc(Et2nPr-AMD)] 47.01 g (0.330 mol) of diethyl-n-propylamidinate was charged into 300 ml of THF, cooled to -78°C, and then 132.2 ml (0.330 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise to prepare Li-(Et2nPr-AMD). The solution was stirred at -78°C for 30 minutes, then warmed to room temperature and stirred further at room temperature for 2 hours. The prepared Li-(Et2nPr-AMD) solution was slowly added dropwise at room temperature to a flask containing (EtCp)2ScCl and stirred at room temperature for 12 hours. The mixture was evaporated under vacuum, dissolved in 250 ml of pentane, filtered, and the solvent and volatiles were evaporated under vacuum. A colorless liquid was obtained by distillation of the resulting red liquid at 150°C and 28.4 mTorr. The yield was 73.33 g (59.6%). 1 The results of the 1H NMR (Bruker AV400MHz HD) analysis are shown in Figure 20. 1 H NMR (C6D6, 25℃): 0.82(t, 3H), 0.98(t, 6H), 1.17(t, 6H), 1.91(q,2H), 2.38(q, 4H), 3.01(q, 4H), 6.0(dt, 8H)

[0094] The pale yellow liquid sample retained 1.2% residual mass during TGA analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min. This result is shown in Figure 21, which represents the percentage of weight loss due to temperature change in the TGA analysis.

[0095] Example 11: Synthesis of bis(isopropylcyclopentadienyl)(diethyl-n-propylamidinate)cerium[(iPrCp)2Ce(Et2nPr-AMD)] 6.13 g (0.256 mol) of NaH and 140 ml of THF were charged into a 500 ml Schlenk flask, and 11.54 g (0.081 mol) of diethyl-n-propylamidinate and 17.56 g (0.162 mol) of isopropylcyclopentadiene were slowly added dropwise at 0°C. The mixture was stirred at room temperature for 12 hours to prepare a mixed solution of Na-EtCp and Na-(Et2Et-AMD). The Schlenk flask containing the reactants was cooled to -10°C, and 20 g (0.081 mol) of cerium chloride was slowly added. After stirring at room temperature for 12 hours, the mixture was evaporated under vacuum. The resulting liquid was purified by distillation at 250°C and 50 mTorr to obtain a dark purple liquid. The yield was 29.5 g (73.4%).

[0096] The dark purple liquid was analyzed using a TGA (SDT Q600, TA Instruments) at a heating rate of 10°C / min in an atmosphere where nitrogen was flowing at 200 ml / min. 1 / 2 The value was 247.4°C, and the residual mass was 1.1% at 350°C, meaning almost nothing was left. These results are shown in Figure 22, which is the TGA analysis result representing the percentage of weight loss due to temperature change.

[0097] The synthesis of the target compound was confirmed by the TGA analysis results, which showed volatilization along a single volatilization curve.

[0098] Furthermore, a dark purple liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes. During DSC analysis (Discovery 25, TA Instruments) performed at a heating rate of 10°C / min, a decomposition peak was observed at 399°C. These results are shown in Figure 23, which represents the DSC analysis results indicating the change in thermal energy due to temperature changes.

[0099] Example 12: Synthesis of bis(ethylcyclopentadienyl)(diethyl-ethylamidinate)gadolinium [(EtCp)2Gd(Et2Et-AMD)] 6.13 g (0.256 mol) of NaH and 140 ml of THF were charged into a 500 ml Schlenk flask, and 11.54 g (0.081 mol) of diethyl-n-propylamidinate and 17.56 g (0.162 mol) of isopropylcyclopentadiene were slowly added dropwise at 0°C. The mixture was stirred at room temperature for 12 hours to prepare a mixed solution of Na-EtCp and Na-(Et2Et-AMD). The Schlenk flask containing the reactants was cooled to -10°C, and 20 g (0.081 mol) of gadolinium chloride was slowly added. After stirring at room temperature for 12 hours, the mixture was evaporated under vacuum. The resulting liquid was purified by distillation at 250°C and 50 mTorr to obtain a pale yellow liquid. The yield was 29.5 g (73.4%).

[0100] The pale yellow liquid was analyzed using a TGA (SDT Q600, TA Instruments) at a heating rate of 10°C / min in an atmosphere where nitrogen was flowing at 200 ml / min. 1 / 2 The value was 224°C, and the residual mass was 2% at 350°C. These results are shown in Figure 24, which represents the percentage of weight loss due to temperature change, based on TGA analysis.

[0101] The synthesis of the target compound was confirmed by the TGA analysis results, which showed volatilization in a single volatilization curve. Furthermore, a pale yellow liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes. During DSC analysis (Discovery 25, TA Instruments) performed at a heating rate of 10°C / min, a decomposition peak was observed at 412°C. These results are shown in Figure 25, which represents the change in thermal energy due to temperature variation in the DSC analysis.

[0102] Furthermore, the pale yellow liquid was analyzed using a viscometer (Brookfield Ametek DV2T viscometer) in a nitrogen atmosphere for viscosity measurement, and it was confirmed to have a low viscosity of 31 cP at 25°C.

[0103] Example 13: Synthesis of bis(ethylcyclopentadienyl)(diethyl-ethylamidinate)dysprosium [(EtCp)2Dy(Et2Et-AMD)] 160 ml of THF, 9.54 g (0.0744 mol) of diethyl-ethylamidinate, and 14.29 g (0.1489 mol) of ethylcyclopentadiene were charged into a 500 ml Schlenk flask and cooled to 0°C. 89.33 ml (0.2233 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise to the cooled solution, and the mixture was stirred at room temperature for 1 hour to prepare a mixed solution of Li-EtCp and Li-(Et2Et-AMD). The Schlenk flask containing the reactants was cooled to 0°C, and 20 g (0.0744 mol) of dysprosium chloride was added. After stirring at room temperature for 3 hours, the mixture was evaporated under vacuum, and the resulting pale green liquid was purified by distillation at 170°C and 58 mTorr to obtain a pale green liquid. The yield was 19.7 g (55.6%).

[0104] The pale green liquid was analyzed using TGA (SDT Q600, TA Instruments) at a heating rate of 10°C / min in an atmosphere where nitrogen was flowing at 200 ml / min. 1 / 2 The value was 225.8°C, and the residual mass was 1.58% at 350°C, meaning almost nothing was left. These results are shown in Figure 26, which represents the percentage of weight loss due to temperature change, based on TGA analysis.

[0105] The synthesis of the target compound was confirmed by the TGA analysis results showing volatilization in a single volatilization curve. Furthermore, during DSC (Discovery 25, TA Instruments) analysis, performed at a heating rate of 10°C / min after maintaining a pale green liquid sample in a sealed DSC container at 40°C for 10 minutes, a decomposition peak was observed at 418°C. These results are shown in Figure 27, which represents the change in thermal energy due to temperature variation in the DSC analysis.

[0106] Furthermore, the pale green liquid was analyzed using a viscometer (Brookfield Ametek DV2T viscometer) in a nitrogen atmosphere for viscosity measurement, and it was confirmed to have a low viscosity of 38 cP at 25°C.

[0107] Example 14: Synthesis of bis(ethylcyclopentadienyl)(diethyl-ethylamidinate)lutetium [(EtCp)2Lu(Et2Et-AMD)] 160 ml of THF, 9.12 g (0.0711 mol) of diethyl-ethylamidinate, and 13.39 g (0.1422 mol) of ethylcyclopentadiene were charged into a 500 ml Schlenk flask and cooled to 0°C. 85.31 ml (0.2133 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise to the cooled solution, and the mixture was stirred at room temperature for 1 hour to prepare a mixed solution of Li-EtCp and Li-(Et2Et-AMD). The Schlenk flask containing the reactants was cooled to 0°C, and 20 g (0.0711 mol) of lutetium chloride was added. After stirring at room temperature for 3 hours, the mixture was evaporated under vacuum, and the resulting brown liquid was purified by distillation at 170°C and 55 mTorr to obtain an orange liquid. The yield was 22.4 g (64.5%). 1 The results of the 1H NMR analysis are shown in Figure 28, and the following characteristic peaks were obtained. 1 H NMR (C6D6, 25℃): 0.83(t, 3H), 0.98(t, 6H), 1.19(q, 6H), 1.93(q,2H), 2.44(q, 4H), 3.00(q, 4H), 6.0(broad, 8H)

[0108] Furthermore, the orange liquid was analyzed using TGA (SDT Q600, manufactured by TA Instruments) at a heating rate of 10°C / min in an atmosphere where nitrogen was flowing at 200 ml / min. 1 / 2 The value was 223°C, and the residual mass was 1.4% at 350°C, indicating that almost nothing was left behind. These results are shown in Figure 29, which represents the percentage of weight loss due to temperature change, based on TGA analysis.

[0109] Furthermore, during DSC (Discovery 25, manufactured by TA Instruments) analysis performed at a heating rate of 10°C / min, after maintaining the orange liquid sample in a sealed DSC container at 40°C for 10 minutes, a decomposition peak was observed at 455°C. These results are shown in Figure 30, which represents the DSC analysis results indicating the change in thermal energy due to temperature changes.

[0110] Furthermore, the orange liquid was analyzed using a viscometer (Brookfield Ametek DV2T viscometer) under a nitrogen atmosphere for viscosity measurement, and it was confirmed to have a low viscosity of 38 cP at 25°C.

[0111] Example 15: Synthesis of tris(diethyl-n-propylamidinate)yttrium [Y(Et2nPr-AMD)3] 9.28 g (0.768 mol) of diethyl-n-propylamidinate was charged into 300 ml of THF, cooled to -78°C, and then 307.3 ml (0.768 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise to prepare Li-(Et2nPr-AMD). The solution was stirred at -78°C for 30 minutes, then warmed to room temperature and stirred further at room temperature for 2 hours. The prepared Li-(Et2nPr-AMD) solution was slowly added dropwise at -78°C to a flask containing YCl3 and stirred at room temperature for 6 hours. The mixture was evaporated under vacuum, dissolved in 250 ml of pentane, filtered, and the solvent and volatiles were evaporated under vacuum. A pale yellow liquid was obtained from the resulting red liquid at 184°C and 31 mTorr. The yield was 107.5 g (81.9%). The NMR analysis results are shown in Figure 31. 1 H NMR (C6D6, 25℃): 0.87(t, 9H), 1.32(t, 18H), 1.52(q, 6H), 2.21(q,6H), 3.24(q, 12H)

[0112] The pale yellow liquid was present at 0.75% during TGA analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass. This result was confirmed by the TGA analysis results (Figure 32), which represent the percentage of weight loss due to temperature change.

[0113] Example 16: Synthesis of tris-(diethyl-n-propylamidinate)terbium [Tb(Et2nPr-AMD)3] In a 500 ml Schlenk flask, 10.0 g (0.0377 mol) of TbCl3 and 50 ml of THF were charged and stirred at room temperature for 4 hours. In a 250 ml Schlenk flask, 50 ml of THF and 16.1 g (0.114 mol) of diethyl-n-propylamidinate were added, cooled to -78 °C, and then 47.5 ml (0.119 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours to produce Li-(Et2nPr-AMD). The produced Li-(Et2nPr-AMD) solution was added dropwise at 0 °C to a flask containing 10 g (0.0377 mol) of TbCl3 and stirred at room temperature for 6 hours. The mixture was filtered to evaporate the solvent and volatile substances under vacuum, and distilled at 220°C and 138 mTorr to obtain a yellow liquid. The yield was 11.0 g (50.1%).

[0114] The yellow liquid was found to be 1.18% during TGA (SDT Q600, TA Instruments) analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass. This result was confirmed by the TGA analysis results, which show the percentage of weight loss due to temperature change, as shown in Figure 33.

[0115] Furthermore, a yellow liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes. During DSC analysis (Discovery 25, TA Instruments Corporation) performed at a heating rate of 10°C / min, a decomposition peak was observed at 417°C. This result was confirmed by the DSC analysis results showing the change in thermal energy due to temperature change, as shown in Figure 34.

[0116] Example 17: Synthesis of tris-(diethyl-n-propylamidinate)dysprosium [Dy(Et2nPr-AMD)3] 10.0 g (0.0372 mol) of DyCl3 and 50 ml of THF were placed in a 500 ml Schlenk flask and stirred at room temperature for 4 hours. 50 ml of THF and 15.9 g (0.112 mol) of diethyl-n-propylamidinate were added to a 250 ml Schlenk flask, cooled to -78°C, and then 46.9 ml (0.117 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours to produce Li-(Et2nPr-AMD). The produced Li-(Et2nPr-AMD) solution was added dropwise at 0°C to a flask containing 10 g (0.0372 mol) of DyCl3 and stirred at room temperature for 6 hours. The mixture was filtered to evaporate the solvent and volatile substances under vacuum, and distilled at 220°C and 90 mTorr to obtain a yellow liquid. The yield was 13.8 g (69%).

[0117] The yellow liquid was found to be 1.59% during TGA (SDT Q600, TA Instruments) analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass. This result was confirmed by the TGA analysis results, which show the percentage of weight loss due to temperature change in Figure 35.

[0118] Furthermore, a yellow liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes. During DSC analysis (Discovery 25, TA Instruments) performed at a heating rate of 10°C / min, a decomposition peak was observed at 487°C. These results were confirmed by the DSC analysis results showing the change in thermal energy due to temperature change, as shown in Figure 36.

[0119] Example 18: Synthesis of tris-(diethyl-n-propylamidinate)erbium [Er(Et2nPr-AMD)3] 10.0 g (0.0365 mol) of ErCl3 and 50 ml of THF were charged into a 500 ml Schlenk flask and stirred at room temperature for 4 hours. 50 ml of THF and 15.6 g (0.110 mol) of diethyl-n-propylamidinate were added to a 250 ml Schlenk flask, cooled to -78°C, and then 46.0 ml (0.115 mol) of n-BuLi-hexane solution (2.5 M) was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours to produce Li-(Et2nPr-AMD). The produced Li-(Et2nPr-AMD) solution was added dropwise at 0°C to a flask containing 10 g (0.0365 mol) of ErCl3 and stirred at room temperature for 6 hours. The mixture was filtered, and the solvent and volatiles were evaporated under vacuum. The mixture was then distilled at 220°C and 80 mTorr to obtain an orange liquid. The yield was 14g (72%).

[0120] The orange liquid was present at 1.52% during TGA (SDT Q600, TA Instruments) analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass. This result was confirmed by the TGA analysis results, which show the percentage of weight loss due to temperature change, as shown in Figure 37.

[0121] Furthermore, after placing the orange liquid sample in a sealed container for DSC and maintaining it at 40°C for 10 minutes, a resolution peak was observed at 466°C during DSC analysis (Discovery 25, TA Instruments) measured at a heating rate of 10°C / min. These results were confirmed by the DSC analysis results showing the change in thermal energy due to temperature change, as shown in Figure 38.

[0122] Furthermore, to confirm the viscosity of the orange liquid, the sample was placed in the measuring container of a rotational viscometer (Brookfield LVD2T) and the viscosity was measured at 25°C using a low-viscosity spindle, confirming a viscosity of 77.1 cPs.

[0123] Example 19: Synthesis of ris-(diethyl-n-propylamidinate)ytterbium [Yb(Et2nPr-AMD)3] 10.0 g (0.0358 mol) of YbCl3 and 50 ml of THF were charged into a 500 ml Schlenk flask and stirred at room temperature for 4 hours. 50 ml of THF and 15.3 g (0.107 mol) of diethyl-n-propylamidinate were added to a 250 ml Schlenk flask, cooled to -78°C, and then 45.1 ml (0.113 mol) of n-BuLi-hexane solution (2.5 M) was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours to produce Li-(Et2nPr-AMD). The produced Li-(Et2nPr-AMD) solution was added dropwise at 0°C to a flask containing 10 g (0.0358 mol) of YbCl3 and stirred at room temperature for 6 hours. The mixture was filtered, and the solvent and volatiles were evaporated under vacuum. The mixture was then distilled at 220°C and 68 mTorr to obtain a yellow liquid. The yield was 14g (70%).

[0124] The yellow liquid was found to be 1.68% during TGA (SDT Q600, TA Instruments) analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass. This result was confirmed by the TGA analysis results, which show the percentage of weight loss due to temperature change, as shown in Figure 39.

[0125] Furthermore, to confirm the viscosity of the yellow liquid, the sample was placed in the measuring container of a rotational viscometer (Brookfield LVD2T), and the viscosity was measured at 25°C using a low-viscosity spindle, resulting in a value of 66.2 cPs.

[0126] Example 20: Synthesis of tris-(diethyl-n-propylamidinate)lutetium [Lu(Et2nPr-AMD)3] 10.0 g (0.0355 mol) of LuCl3 and 50 ml of THF were charged into a 500 ml Schlenk flask and stirred at room temperature for 4 hours. 50 ml of THF and 15.2 g (0.107 mol) of diethyl-n-propylamidinate were added to a 250 ml Schlenk flask, cooled to -78°C, and then 44.8 ml (0.112 mol) of n-BuLi-hexane solution (2.5 M) was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours to produce Li-(Et2nPr-AMD). The produced Li-(Et2nPr-AMD) solution was added dropwise at 0°C to a flask containing 10 g (0.0355 mol) of LuCl3 and stirred at room temperature for 6 hours. The mixture was filtered, and the solvent and volatiles were evaporated under vacuum. The mixture was then distilled at 220°C and 54 mTorr to obtain an orange liquid. The yield was 16.2g (75.8%). 1 The results of the 1H NMR analysis are shown in Figure 40. 1 H NMR (C6D6, 25℃): 0.88(t, 9H), 1.30(t, 18H), 1.51(q, 6H), 2.21(q, 6H), 3.28(q, 12H)

[0127] The orange liquid was found to be 0.95% during TGA (TA Instruments SDT Q600) analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass. This result was confirmed by the TGA analysis results, which show the percentage of weight loss due to temperature change, as shown in Figure 41.

[0128] Furthermore, after placing the orange liquid sample in a sealed container for DSC and maintaining it at 40°C for 10 minutes, a resolution peak was observed at 442°C during DSC analysis (Discovery 25, TA Instruments) measured at a heating rate of 10°C / min. These results were confirmed by the DSC analysis results showing the change in thermal energy due to temperature change, as shown in Figure 42.

[0129] Example 21: Production of (CH2CH2CH2N-C(CH2CH3)=N-CH2CH2CH3)2Hf(DMA)2 Under a nitrogen atmosphere, 2.8 g (0.0080 mol) of tetrakis(dimethylamino)hafnium (Hf(NMe2)4) and 50 ml of n-hexane were added to a 250 ml Schlenk flask. 2.5 g (0.0160 mol) of (E)-N,N'-dipropylpropionimidamide was slowly added dropwise at room temperature, and the mixture was stirred at room temperature for 14 hours. After the reaction was complete, the resulting reaction mixture was reduced in pressure to remove the solvent and volatile by-reactants. The remaining liquid was purified at 126.6 °C (63.4 mTorr) to obtain 1 g (yield 21.7%) of a pale yellow viscous liquid compound 1. 1 The results of the 1H NMR analysis are shown in Figure 43. 1 H NMR (C6D6, 25℃): 3.326(s, 12H), 3.23(t, 8H), 2.00(q, 4H), 1.64(m, 8H), 0.96(t, 12H), 0.93(t, 6H)

[0130] The pale yellow liquid was found to be 0.95% during TGA (SDT Q600, TA Instruments) analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass. This result was confirmed by the TGA analysis results, which show the percentage of weight loss due to temperature change, as shown in Figure 44(a).

[0131] Furthermore, after placing the orange liquid sample in a sealed container for DSC and maintaining it at 40°C for 10 minutes, a resolution peak was observed at 351°C during DSC analysis (Discovery 25, TA Instruments) measured at a heating rate of 10°C / min (Figure 44(b)).

[0132] Example 22: Production of (CH2CH2N-C(CH2CH2CH3)=N-CH2CH3)2Hf(DMA)2 Under a nitrogen atmosphere, 3.1 g (0.0088 mol) of tetrakis(dimethylamino)hafnium (Hf(NMe2)4) and 50 ml of n-hexane were charged into a 250 ml Schlenk flask. 2.5 g (0.0176 mol) of (E)-N,N'-diethylpropylbutyrimidamide was slowly added dropwise at room temperature, and the mixture was stirred at room temperature for 14 hours. After the reaction was complete, the resulting reaction mixture was reduced in pressure to remove the solvent and volatile by-reactants. The remaining liquid was purified at 117.2 °C (54.3 mTorr) to obtain 2 g (41.7% yield) of pale yellow liquid compound 3. 1 The results of the 1H NMR analysis are shown in Figure 45. 1 H NMR (C6D6, 25℃): 3.345(s, 12H), 3.31(q, 8H), 2.02(m, 4H), 1.44(m, 4H), 1.19(t, 12H), 0.83(t, 6H)

[0133] The pale yellow liquid was found to be 0.53% during TGA (SDT Q600, TA Instruments) analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass. This result was confirmed by the TGA analysis results, which show the percentage of weight loss due to temperature change, as shown in Figure 46(a).

[0134] Furthermore, after placing the pale yellow sample in a sealed container for DSC and maintaining it at 40°C for 10 minutes, a decomposition peak was observed at 330°C during DSC analysis (Discovery 25, TA Instruments) measured at a heating rate of 10°C / min (Figure 46(b)).

[0135] Example 23: Production of (CH2CH2N-C(CH2CH2CH3)=N-CH2CH3)2Hf(EMA)2 Under a nitrogen atmosphere, 3.6 g (0.0080 mol) of tetrakis(ethylmethylamino)hafnium (Hf(NEtMe)4) and 50 ml of n-hexane were charged into a 250 ml Schlenk flask. 2.5 g (0.0176 mol) of (E)-N,N'-diethylpropylbutyrimidamide was slowly added dropwise at room temperature, and the mixture was stirred at room temperature for 14 hours. After the reaction was complete, the resulting reaction mixture was reduced in pressure to remove the solvent and volatile by-reactants. The remaining liquid was purified at 123.4 °C (25.3 mTorr) to obtain 2 g (39.2% yield) of pale yellow liquid compound 4. 1 The results of the 1H NMR analysis are shown in Figure 47. 1 H NMR (C6D6, 25℃): 3.63(q, 4H), 3.33(q, 8H), 3.32(s, 6H), 2.20(m,4H), 1.46(m, 4H), 1.25(q, 6H), 1.20(t, 12H), 0.08(t, 6H)

[0136] The pale yellow liquid was found to be 0.95% during TGA (SDT Q600, TA Instruments) analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass. This result was confirmed by the TGA analysis results, which show the percentage of weight loss due to temperature change, as shown in Figure 48(a).

[0137] Furthermore, a pale yellow liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes. During DSC analysis (Discovery 25, TA Instruments Corporation) performed at a heating rate of 10°C / min, a decomposition peak was observed at 339°C (Figure 48(b)).

[0138] Example 24: Production of (CH2CH2N-C(CH2CH2CH3)=N-CH2CH3)2Zr(DMA)2 Under a nitrogen atmosphere, 4 g (0.0150 mol) of tetrakis(dimethylamino)zirconium (Zr(NMe2)4) and 50 ml of n-hexane were charged into a 250 ml Schlenk flask. 4.3 g (0.0300 mol) of (E)-N,N'-diethylpropylbutyrimidamide was slowly added dropwise at room temperature, and the mixture was stirred at room temperature for 14 hours. After the reaction was complete, the resulting reaction solution was reduced in pressure to remove the solvent and volatile by-reactants. The remaining liquid was purified at 116.2 °C (67.8 mTorr) to obtain 2.9 g (42.0% yield) of pale yellow liquid compound 5. 1 The results of the 1H NMR analysis are shown in Figure 49. 1 H NMR (C6D6, 25℃): 3.27(q, 8H), 3.261(s, 12H), 2.05(m, 4H), 1.45(m, 4H), 1.21(t, 12H), 0.84(t, 6H)

[0139] The pale yellow liquid was found to be 0.95% during TGA (SDT Q600, TA Instruments) analysis, measured at a heating rate of 10°C / min in an atmosphere of nitrogen flowing at 200 ml / min, leaving virtually no residual mass. This result was confirmed by the TGA analysis results, which show the percentage of weight loss due to temperature change, as shown in Figure 50(a).

[0140] Furthermore, a pale yellow liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes. During DSC analysis (Discovery 25, TA Instruments Corporation) performed at a heating rate of 10°C / min, a decomposition peak was observed at 304°C (Figure 50(b)).

[0141] Example 25: Preparation of (2-ethyl-N,N-diethylamidinate)bis(dimethylamino)borane [(Et2Et-AMD)B(DMA)2] In reaction vessel 1, 5.9 g (0.04 mol) of tris(dimethylamino)borane (TDMAB) was diluted with 30 ml of hexane and cooled to cryogenic temperature (approximately -20°C). Then, 2 ml (0.02 mol) of tribromoboron (BBr3) was added, and the mixture was stirred at room temperature for approximately 6 hours. In reaction vessel 2, 7.98 g (0.06 mol) of 2-ethyl-N,N-diethylamidinate was diluted with 30 ml of hexane and cooled to cryogenic temperature (approximately -20°C). Then, 24.9 ml (0.06 mol) of 2.5 M n-butyllithium (n-BuLi) was slowly added, and the mixture was stirred at room temperature for approximately 6 hours. After recooling reaction vessel 1 to cryogenic temperatures (approximately -20°C), the solution from reaction vessel 2 was slowly transferred and added, and the mixture was stirred at room temperature for approximately 12 hours. The reactants were filtered, and the solvent was removed from the filtrate under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure to yield 8.5 g (yield: 61%). 1 The results of the 1H NMR analysis are shown in Figure 51. 11 The results of the 1B NMR analysis are shown in Figure 52. 1 H NMR (C6D6, 25℃): 0.96 (t, 3H), 1.36(t, 6H), 2.13(q, 2H), 2.44(s, 12H), 3.49(q, 4H) 11 B-NMR: 28.09 ppm

[0142] Example 26: Preparation of (2-methyl-N,N-diisopropylamidinate)bis(dimethylamino)borane [(iPr2Me-AMD)B(DMA)2] In reaction vessel 1, 5.9 g (0.04 mol) of tris(dimethylamino)borane (TDMAB) was diluted with 20 ml of hexane and cooled to cryogenic temperature (approximately -20°C). Then, 2 ml (0.02 mol) of tribromoboron (BBr3) was added, and the mixture was stirred at room temperature for approximately 6 hours. In reaction vessel 2, 0.86 g (0.06 mol) of N,N-diisopropylcarbodiimide was diluted with 20 ml of hexane and cooled to cryogenic temperature (approximately -20°C). Then, 42.8 ml (0.06 mol) of 1.6 M methyl lithium (MeLi) was slowly added, and the mixture was stirred at room temperature for approximately 6 hours. After recooling reaction vessel 1 to cryogenic temperature (approximately -20°C), the solution from reaction vessel 2 was slowly transferred and added, and the mixture was stirred at room temperature for approximately 12 hours. The solvent in the filtrate obtained by filtering the reaction products was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [82.5℃@1 torr] to obtain 7.5 g of colorless liquid (yield: 50%). 1 The results of the 1H NMR analysis are shown in Figure 53. 11 The results of the 1B NMR analysis are shown in Figure 54. 1 H NMR (C6D6, 25℃): 1.31(d, 12H), 1.60(s, 3H), 2.43(s, 12H), 4.05(m, 2H) 11 B-NMR: 28.07 ppm

[0143] Example 27: Preparation of (2-ethyl-N,N-diethylamidinate)(N,N-dimethylethylenediamino)borane [(Et2Et-AMD)B(DMA-EDA)] 79 ml (0.56 mol) of triethylamine was diluted with 200 ml of hexane and cooled to a low temperature (approximately 0°C). A solution of 26.9 ml (0.28 mol) of tribromoboron (BBr3) diluted with 40 ml of hexane was added and the mixture was stirred at room temperature for approximately 2 hours. A solution of 25 g (0.28 mol) of N,N-dimethylethylenediamine diluted with 100 ml of hexane was added and the mixture was heated and stirred for approximately 3 hours. The reaction product was filtered, and the solvent of the filtrate was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [51.5°C @ 40 torr] to obtain 23 g (yield: 69%) of a colorless liquid intermediate. 1 H NMR (C6D6, 25℃): 2.49 (s, 6H,) 2.76 (s, 4H) 11 1B-NMR: 26.32 ppm

[0144] In reaction vessel 2, 3.62 g (0.02 mol) of 2-ethyl-N,N-diethylamidinate was diluted in 30 ml of hexane and cooled to cryogenic temperature (approximately -20°C). Then, 11.3 ml (0.02 mol) of 2.5 M n-butyl lithium (n-BuLi) was slowly added, and the mixture was stirred at room temperature for approximately 6 hours. In reaction vessel 1, 5 g (0.02 mol) of the aforementioned 2-bromo-1,3-dimethyl-1,3,2-diazaborolane was diluted in 10 ml of hexane and cooled to cryogenic temperature (approximately -20°C). Then, the solution from reaction vessel 2 was slowly transferred and added, and the mixture was stirred at room temperature for approximately 12 hours. The reactants were filtered, and the solvent of the filtrate was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [63.3℃@1 torr] to obtain 3.6 g of a colorless liquid (yield: 60%). 1 The results of the 1H NMR analysis are shown in Figure 55. 11 The results of the 1B NMR analysis are shown in Figure 56. 1 H NMR (C6D6, 25℃): 1.01(t, 3H), 1.35(t, 6H), 2.19(q, 2H), 2.42(s, 6H), 2.88 (s, 4H), 3.52(q, 4H) 11 B-NMR: 28.31 ppm

[0145] Example 28: Preparation of (N-ethyl-2-isobutyl-N-propylamidinate)bis(dimethylamino)borane [(EtPrisoBu-AMD)B(DMA)2] In reaction vessel 1, 5.9 g (0.04 mol) of tris(dimethylamino)borane (TDMAB) was diluted with 15 ml of hexane, cooled to cryogenic temperature (approximately -20°C), and then 2 ml (0.02 mol) of tribromoboron (BBr3) was added. The mixture was stirred at room temperature for approximately 6 hours. In reaction vessel 2, 10.6 g (0.06 mol) of N-ethyl-2-isobutyl-N-propylamidinate was diluted with 30 ml of hexane, cooled to cryogenic temperature (approximately -20°C), and then 24.9 ml (0.06 mol) of 2.5 M n-butyl lithium (n-BuLi) was slowly added. The mixture was stirred at room temperature for approximately 6 hours. After recooling reaction vessel 1 to cryogenic temperatures (approximately -20°C), the solution from reaction vessel 2 was slowly transferred and added, and the mixture was stirred at room temperature for approximately 12 hours. The reactants were filtered, and the solvent was removed from the filtrate under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [83.7°C @ 0.1 torr] to obtain 12.4 g of colorless liquid (yield: 74%). 1 The results of the 1H NMR analysis are shown in Figure 57. 11 The results of the 1B NMR analysis are shown in Figure 58. 1H NMR (C6D6, 25℃): 0.90(d, 6H), 1.06(t, 3H), 1.33(t, 3H), 1.82 (m, 3H), 2.11(d, 2H), 2.45(s, 12H), 3.41(t, 2H), 3.49(q, 2H) 11 B-NMR: 28.25 ppm

[0146] These experimental results confirm that, in a structure to which the novel amidinate ligand according to the present invention is applied, a liquid precursor with sufficient vapor pressure and thermal stability for use as a semiconductor precursor can be obtained, and in particular, the viscosity characteristics of the precursor were greatly improved.

[0147] Although the present invention has been described with reference to preferred embodiments as described above, it is not limited to these embodiments, and various modifications and alterations are possible by those with ordinary skill in the art to which the invention pertains without departing from the spirit of the invention. Such modifications and alterations should be understood to be within the scope of the present invention and the appended claims.

Claims

1. A precursor for forming thin films, comprising a compound represented by the following chemical formula 1, The aforementioned thin film formation precursor is characterized by being liquid at room temperature. [Chemical formula 1] (L) ｎ -M-(AMD) ｍ (In the above chemical formula 1, AMD is an amidinate ligand, M is the central metal atom, and is one of the elements from Groups 2 to 6, Group 13, Group 15, transition metals, and rare earth elements. L is a ligand that is the same as or different from AMD, and if it is different from AMD, it is one of a substituted or unsubstituted cyclopentadienyl group, amine, alcohol, alkyl, aryl, aminoamine, alkoxyamine, amino alcohol, alkoxy alcohol, imide, diamine, dialcohol, formidinate, guanidinate, beta-diketonate, ketoiminate, amide, and halide. n is an integer between 0 and 5. m is an integer between 1 and 6.

2. The thin-film forming precursor according to claim 1, characterized in that the AMD is a ligand represented by the following chemical formula 2. [Chemical formula 2] 【Chemistry 1】 (In the above chemical formula 2, R １ and R ３ Each of them is independent of C １ ~C ５ These are linear, branched, or cyclic alkyl or alkenyl groups. R ２ is a hydrogen atom or a linear, branched or cyclic alkyl or alkenyl group of C １ to C ５ .)

3. In the above chemical formula 2, the R ２ C ２ ~C ５ The thin film forming precursor according to claim 2, characterized by being a linear, branched, or cyclic alkyl or alkenyl group.

4. In the above chemical formula 2, the R １ and R ３ Each of them is independent of C ２ ~C ５ The R is a linear, branched, or cyclic alkyl or alkenyl group, and ２ C ２ ~C ５ The thin-film forming precursor according to claim 2, characterized by being a linear, branched, or cyclic alkyl group or alkenyl group.

5. In the above chemical formula 2, the R １ and R ３ The precursor for thin film formation according to claim 2, characterized in that it is a methyl group.

6. In the above chemical formula 2, the R ２ The precursor for thin film formation according to claim 2, characterized in that is an isopropyl group.

7. In the above chemical formula 2, the R １ and R ３ Each of them is independent of C １ ~C ５ The thin film forming precursor according to claim 2, characterized by being a linear alkyl group or alkenyl group.

8. In the above chemical formula 2, the R １ and R ３ Each of them is independent of C １ ~C ５ The linear alkyl or alkenyl group is R ２ C １ ~C ５ The thin film forming precursor according to claim 2, characterized by being a linear alkyl group or alkenyl group.

9. In the above chemical formula 2, the R １ and R ３ They are all identical, C １ ~C ５ The thin-film forming precursor according to claim 2, characterized by being a linear, branched, or cyclic alkyl group or alkenyl group.

10. In the above chemical formula 2, the R １ ~R ３ They are all identical, C １ ~C ４ The thin-film forming precursor according to claim 2, characterized by being a linear, branched, or cyclic alkyl group or alkenyl group.

11. The thin-film forming precursor according to claim 2, characterized in that the amidinate ligand is one or more selected from the following chemical structures. 【Chemistry 2】 【change】

12. The thin film forming precursor according to claim 1, characterized in that the thin film forming precursor has a viscosity of 60 cP (25°C) or less.

13. The precursor for thin film formation according to claim 1, characterized in that the compound represented by the chemical formula 1 is one or more selected from the following chemical structures. 【Transformation 3】 【change】

14. The precursor for thin film formation according to claim 1, characterized in that the compound represented by the chemical formula 1 is one or more selected from the following chemical structures. 【Chemistry 4】 【change】 【change】 【change】

15. The precursor for thin film formation according to claim 1, characterized in that the compound represented by the chemical formula 1 is one or more selected from the following chemical structures. 【Transformation 5】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】

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