Precursor for forming thin film comprising amidinate ligand

Abstract

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

Description

A precursor for forming a thin film comprising an amidinate ligand.

[0001] The present invention relates to a precursor for forming a thin film comprising an amidinate ligand, and more particularly, to a precursor for forming a thin film comprising an amidinate ligand, which comprises a novel amidinate ligand, thereby forming a precursor having low viscosity, high heat resistance, high volatility, and being liquid at room temperature, and thereby enabling the formation of a high-quality thin film.

[0002] As integration increases through miniaturization of semiconductor device line widths, the available space for implementing capacitor structures is constrained by line width. This has led to limitations in the manufacturing of semiconductor devices for capacitor structures using existing methods. In particular, the application of high-k thin films has led to a significant deterioration in leakage current due to the bandgap. One solution to this problem requires technology for forming high-quality thin films, and for this purpose, optimization of the precursors used in thin film formation is necessary.

[0003] Precursors for thin film formation are composed of a central metal atom and a ligand. Since chemical properties such as viscosity, heat resistance, and volatility vary depending on the structure of the ligand, precursors with various types of ligands combined are being developed taking this into consideration.

[0004] For example, Korean Patent Registration No. 10-1660052, Korean Patent Publication No. 10-2019-0109142, and Korean Patent Publication No. 10-2021-0084297 disclose chemical structures in which cyclopentadienyl and amidinate are bonded as ligands as precursors containing yttrium or a lanthanide metal. These ligand-bonded precursors are reported to be suitable for thin film formation processes because they can improve upon the shortcomings of existing yttrium or lanthanide metal precursors, such as low vapor pressure and high viscosity.

[0005] However, these conventional precursors still have high viscosity, which can cause various problems in the semiconductor thin film formation process. Therefore, there is a need to develop precursors that exhibit the chemical properties (e.g., liquid phase, high volatility, high heat resistance) required for the semiconductor thin film formation process, while also improving viscosity characteristics. In particular, referring to the results of prior art, chemical structures containing amidinates as ligands are expected to achieve the chemical properties of precursors required for the thin film formation process.

[0006] The present invention has been conceived in consideration of the above-described prior arts, and its purpose is to provide a precursor for forming a thin film including a novel amidinate ligand.

[0007] In addition, the purpose is to provide a precursor for forming a thin film that exhibits chemical properties such as low viscosity, high heat resistance, and high volatility, including the above ligand.

[0008] The precursor for forming a thin film of the present invention to achieve the above purpose comprises a compound represented by the following chemical formula 1, and is characterized in that it is liquid at room temperature.

[0009]

[0010] [Chemical Formula 1]

[0011] (L) n -M-(AMD) m

[0012]

[0013] In the above chemical formula 1, AMD is an amidinate ligand, M is a central metal atom, which is any one of a group 2 to 6 element, a group 13 element, a group 15 element, a transition metal, and a rare earth element, L is a ligand which is the same as or different from the AMD, and when different from the AMD, is any one of a substituted or unsubstituted cyclopentadienyl group, amine, alcohol, alkyl, aryl, amino amine, alkoxy amine, amino alcohol, alkoxy alcohol, imido, diamine, dialcohol, formidinate, guanidinate, beta-diketonate, ketoiminate, amide, and halide, n is an integer of 0 to 5, and m is an integer of 1 to 6.

[0014] At this time, the AMD may be a ligand represented by the following chemical formula 2.

[0015] [Chemical Formula 2]

[0016]

[0017] In the above chemical formula 2, R1 and R3 are each independently a C1-C5 straight-chain, branched or cyclic alkyl group or alkenyl group, and R2 is a hydrogen atom or a C1-C5 straight-chain, branched or cyclic alkyl group or alkenyl group.

[0018] In addition, in the above chemical formula 2, R2 may be a C2-C5 straight-chain, branched or cyclic alkyl group or alkenyl group.

[0019] In addition, in the above chemical formula 2, R1 and R3 are each independently a C2-C5 straight-chain, branched or cyclic alkyl group or alkenyl group, and R2 may be a C2-C5 straight-chain, branched or cyclic alkyl group or alkenyl group.

[0020] Additionally, in the above chemical formula 2, R1 and R3 may be methyl groups.

[0021] Additionally, in the above chemical formula 2, R2 may be an isopropyl group.

[0022] In addition, in the above chemical formula 2, R1 and R3 may each independently be a C1-C5 straight-chain alkyl group or alkenyl group.

[0023] In addition, in the above chemical formula 2, R1 and R3 are each independently a C1-C5 straight-chain alkyl group or alkenyl group, and R2 may be a C1-C5 straight-chain alkyl group or alkenyl group.

[0024] In addition, in the above chemical formula 2, R1 and R3 are both the same and may be a C1-C5 straight-chain, branched or cyclic alkyl group or alkenyl group.

[0025] In addition, in the above chemical formula 2, R1 to R3 are all the same and may be a C1-C4 straight-chain, branched or cyclic alkyl group or alkenyl group.

[0026] In addition, it is preferable that the precursor for forming the thin film is a low-viscosity precursor having a viscosity of 60 cP (25°C) or less.

[0027] The precursor for forming a thin film according to the present invention can exhibit high structural stability, low viscosity, high volatility, high heat resistance, and chemical properties of a room-temperature liquid form of the precursor compound by including an amidinate ligand.

[0028] Therefore, the precursor for forming a thin film including the amidinate ligand exhibits properties suitable for use in a thin film forming process, and thus can form a high-quality thin film without thermal decomposition during the process or residual issues in a pipe due to high viscosity, and can provide a semiconductor device including a thin film manufactured by the thin film forming method.

[0029] Figure 1 shows the diethyl-ethylamidinate ligand. 1 This is the result of H-NMR analysis.

[0030] Figure 2 shows the TGA analysis results of the diethyl-ethylamidinate ligand.

[0031] Figure 3 shows the diethyl-normal propyl amidinate ligand. 1This is the result of H-NMR analysis.

[0032] Figure 4 shows the TGA analysis results of diethyl-normal propyl amidinate ligand.

[0033] Figure 5 shows the structure of the dinormal propyl-ethylamidinate ligand. 1 This is the result of H-NMR analysis.

[0034] Figure 6 shows the TGA analysis results of the dinormal propyl-ethylamidinate ligand.

[0035] Figure 7 is a schematic diagram of bis(ethylcyclopentadienyl)(diethyl-ethylamidinato)yttrium. 1 This is the result of H-NMR analysis.

[0036] Figure 8 shows the TGA analysis results of bis(ethylcyclopentadienyl)(diethyl-ethylamidinato)yttrium.

[0037] Figure 9 shows the DSC analysis results of bis(ethylcyclopentadienyl)(diethyl-ethylamidinato)yttrium.

[0038] Figure 10 is a schematic diagram of bis(ethylcyclopentadienyl)(diethyl-normal-propylamidinato)yttrium. 1 This is the result of H-NMR analysis.

[0039] Figure 11 shows the TGA analysis results of bis(ethylcyclopentadienyl)(diethyl-normal-propylamidinato)yttrium.

[0040] Figure 12 is a schematic diagram of bis(isopropylcyclopentadienyl)(diethyl-ethylamidinato)yttrium. 1 This is the result of H-NMR analysis.

[0041] Figure 13 is a schematic diagram of bis(methylcyclopentadienyl)(diethyl-normal-propylamidinato)yttrium. 1 This is the result of H-NMR analysis.

[0042] Figure 14 shows the TGA analysis results of bis(methylcyclopentadienyl)(diethyl-normal-propylamidinato)yttrium.

[0043] Figure 15 is a schematic diagram of bis(methylcyclopentadienyl)(dinormalpropyl-ethylamidinato)yttrium. 1 This is the result of H-NMR analysis.

[0044] Figure 16 shows the TGA analysis results of bis(methylcyclopentadienyl)(dinormalpropyl-ethylamidinato)yttrium.

[0045] Figure 17 is a schematic diagram of bis(ethylcyclopentadienyl)(dimethyl-propylamidinato)yttrium. 1 This is the result of H-NMR analysis.

[0046] Figure 18 shows the TGA analysis results of bis(ethylcyclopentadienyl)(dimethyl-propylamidinato)yttrium.

[0047] Figure 19 shows the DSC analysis results of bis(ethylcyclopentadienyl)(dimethyl-propylamidinato)yttrium.

[0048] Figure 20 is a schematic diagram of bis(ethylcyclopentadienyl)(diethyl-normal-propylamidinato) scandium. 1 This is the result of H-NMR analysis.

[0049] Figure 21 shows the TGA analysis results of bis(ethylcyclopentadienyl)(diethyl-normal-propylamidinato) scandium.

[0050] Figure 22 shows the TGA analysis results of bis(isopropylcyclopentadienyl)(diethyl-normal-propylamidinato)cerium.

[0051] Figure 23 shows the DSC analysis results of bis(isopropylcyclopentadienyl)(diethyl-normal-propylamidinato)cerium.

[0052] Figure 24 shows the TGA analysis results of bis(ethylcyclopentadienyl)(diethyl-ethylamidinato)gadolinium.

[0053] Figure 25 shows the DSC analysis results of bis(ethylcyclopentadienyl)(diethyl-ethylamidinato)gadolinium.

[0054] Figure 26 shows the TGA analysis results of bis(ethylcyclopentadienyl)(diethyl-ethylamidinato) disprosium.

[0055] Figure 27 shows the DSC analysis results of bis(ethylcyclopentadienyl)(diethyl-ethylamidinato) disprosium.

[0056] Figure 28 is a diagram of bis(ethylcyclopentadienyl)(diethyl-ethylamidinato)lutetium. 1 This is the result of H-NMR analysis.

[0057] Figure 29 shows the TGA analysis results of bis(ethylcyclopentadienyl)(diethyl-ethylamidinato)lutetium.

[0058] Figure 30 shows the DSC analysis results of bis(ethylcyclopentadienyl)(diethyl-ethylamidinato)lutetium.

[0059] Figure 31 is a diagram of tris(diethyl-normal-propyladiene)yttrium. 1 This is the result of H-NMR analysis.

[0060] Figure 32 shows the TGA analysis results of tris(diethyl-normal-propyladiene)yttrium.

[0061] Figure 33 shows the TGA analysis results of tris-(diethyl-n-propylamidinato)terbium.

[0062] Figure 34 shows the DSC analysis results of tris-(diethyl-n-propylamidinato)terbium.

[0063] Figure 35 shows the TGA analysis results of tris-(diethyl-n-propylamidinato)diceprosium.

[0064] Figure 36 shows the DSC analysis results of tris-(diethyl-n-propylamidinato)diceprosium.

[0065] Figure 37 shows the TGA analysis results of tris-(diethyl-n-propylamidinato)erbium.

[0066] Figure 38 shows the DSC analysis results of tris-(diethyl-n-propylamidinato)erbium.

[0067] Figure 39 shows the TGA analysis results of tris-(diethyl-n-propylamidinato)ytterbium.

[0068] Figure 40 is a diagram of tris-(diethyl-n-propylamidinato)lutetium. 1 This is the result of H-NMR analysis.

[0069] Figure 41 shows the TGA analysis results of tris-(diethyl-n-propylamidinato)lutetium.

[0070] Figure 42 shows the DSC analysis results of tris-(diethyl-n-propylamidinato)lutetium.

[0071] Figure 43 is (CH2CH2CH2N-C(CH2CH3)=N-CH2CH2CH3)2Hf(DMA)2 1 This is the result of H-NMR analysis.

[0072] Figure 44 shows the TGA (a) and DSC (b) analysis results of (CH2CH2CH2N-C(CH2CH3)=N-CH2CH2CH3)2Hf(DMA)2.

[0073] Fig. 45 is (CH2CH2N-C(CH2CH2CH3)=N-CH2CH3)2Hf(DMA)2 1 This is the result of H-NMR analysis.

[0074] Figure 46 shows the TGA (a) and DSC (b) analysis results of (CH2CH2N-C(CH2CH2CH3)=N-CH2CH3)2Hf(DMA)2.

[0075] Figure 47 is (CH2CH2N-C(CH2CH2CH3)=N-CH2CH3)2Hf(EMA)2 1 This is the result of H-NMR analysis.

[0076] Figure 48 shows the TGA (a) and DSC (b) analysis results of (CH2CH2N-C(CH2CH2CH3)=N-CH2CH3)2Hf(EMA)2.

[0077] Fig. 49 is (CH2CH2N -C(CH2CH2CH3)=N- CH2CH3)2Zr(DMA)2 1 This is the result of H-NMR analysis.

[0078] Figure 50 shows the TGA (a) and DSC (b) analysis results of (CH2CH2N -C(CH2CH2CH3)=N- CH2CH3)2Zr(DMA)2.

[0079] Figure 51 is (2-ethyl-N,N-diethylamidinato)bis(dimethylamino)borane. 1 This is the result of H NMR analysis.

[0080] Figure 52 is (2-ethyl-N,N-diethylamidinato)bis(dimethylamino)borane. 11 This is the result of B NMR analysis.

[0081] Figure 53 is (2-methyl-N,N-diisopropylamidinato)bis(dimethylamino)borane. 1 This is the result of H NMR analysis.

[0082] Figure 54 is (2-methyl-N,N-diisopropylamidinato)bis(dimethylamino)borane. 11 This is the result of B NMR analysis.

[0083] Figure 55 is (2-ethyl-N,N-diethylamidinato)(N,N-dimethylethylenediamino)borane. 1 This is the result of H NMR analysis.

[0084] Figure 56 is (2-ethyl-N,N-diethylamidinato)(N,N-dimethylethylenediamino)borane. 11 This is the result of B NMR analysis.

[0085] Figure 57 is a diagram of (N-ethyl-2-isobutyl-N-propylamidinato)bis(dimethylamino)borane. 1 This is the result of H NMR analysis.

[0086] Figure 58 is (N-ethyl-2-isobutyl-N-propylamidinato)bis(dimethylamino)borane. 11 This is the result of B NMR analysis.

[0087] The present invention will be described in more detail below. Terms and words used in this specification and claims should not be construed as limited to their conventional or dictionary meanings. Rather, they should be interpreted in a way that is consistent with the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of a term to best explain his or her invention.

[0088] A precursor for forming a thin film according to the present invention comprises a compound represented by the following chemical formula 1, and is characterized in that it is liquid at room temperature.

[0089] [Chemical Formula 1]

[0090] (L) n -M-(AMD) m

[0091] In the above chemical formula 1, AMD is an amidinate ligand, M is a central metal atom, which is any one of a group 2 to 6 element, a group 13 element, a group 15 element, a transition metal, and a rare earth element, L is a ligand which is the same as or different from the AMD, and when different from the AMD, is any one of a substituted or unsubstituted cyclopentadienyl group, amine, alcohol, alkyl, aryl, amino amine, alkoxy amine, amino alcohol, alkoxy alcohol, imido, diamine, dialcohol, formidinate, guanidinate, beta-diketonate, ketoiminate, amide, and halide, n is an integer of 0 to 5, and m is an integer of 1 to 6.

[0092] Additionally, a ligand compound represented by the following chemical formula 2 can be applied to the above AMD.

[0093] [Chemical Formula 2]

[0094]

[0095] In the above chemical formula 2, R1 and R3 are each independently a C1-C5 straight-chain, branched or cyclic alkyl group or alkenyl group, and R2 is a hydrogen atom or a C1-C5 straight-chain, branched or cyclic alkyl group or alkenyl group.

[0096] The above amidinate ligand is used as a ligand of a precursor compound for forming a thin film of the present invention, and in particular, R1 and R3 in the above amidinate ligand may be the same or different, and may be configured in various forms depending on the desired effect of the precursor in which the ligand is included.

[0097] In addition, in the above chemical formula 2, R2 may be a hydrogen atom, or a C1-C5 straight-chain, branched, or cyclic alkyl group or alkenyl group, and as a non-limiting example, R2 may include an n-alkyl group such as an ethyl group, a propyl group, or a butyl group.

[0098] The precursor comprising the amidinate ligand represented by the above chemical formula 2 has low viscosity, high thermal stability and volatility, and can be in a liquid form at room temperature, and thus it was found that the chemical properties of the desired precursor can be obtained through the synthesis of the precursor comprising the above ligand. That is, since it exhibits overall improved physical properties compared to various precursor compounds comprising the amidinate ligand of the prior art, it is possible to obtain improved effects as a precursor and in a thin film formation process using the precursor.

[0099] The amidinate ligand represented by the above chemical formula 2 can form a form in which various functional groups are combined.

[0100] In one embodiment, the R2 may be a C2-C5 straight-chain, branched, or cyclic alkyl or alkenyl group. When the R2 is provided as C2 or more, structural asymmetry may be increased while minimizing intramolecular structural steric hindrance compared to when it is H or C1, thereby reducing intermolecular mutual interference. Therefore, the precursor including the ligand can be easily formed into a liquid form and also obtain low viscosity characteristics.

[0101] Meanwhile, the above R1 and R3 are each independently a C2-C5 straight-chain, branched or cyclic alkyl group or alkenyl group, and the above R2 may be a C2-C5 straight-chain, branched or cyclic alkyl group or alkenyl group.

[0102] In another embodiment, R1 and R3 may be methyl groups, and R2 may be an isopropyl group.

[0103] In addition, the above R1 and R3 may each independently be a C1-C5 straight-chain alkyl group or alkenyl group.

[0104] A straight-chain alkyl group or alkenyl group can achieve the effect of improving volatility and vapor pressure by reducing the molecular weight through structural minimization of the ligand compared to a branched or cyclic group. Therefore, in the ligand according to one embodiment of the present invention, each of R1 and R3 may be composed of a straight-chain alkyl group or alkenyl group, and in this case, the precursor for forming a thin film including the ligand has an improved vapor pressure, which can lead to the provision of effects such as ease of process during a thin film forming process using the precursor.

[0105] In addition to the effect of improving vapor pressure, the ligand in which each of R1 and R3 is composed of a straight-chain alkyl group can provide an effect of improving the degree of freedom of the precursor to which the ligand is applied because the ligand has a high degree of structural freedom. This effect minimizes the indirectness between precursors, thereby producing the characteristics of liquefaction and low viscosity of the precursor.

[0106] Therefore, the amidinate ligand according to one embodiment may be composed of R1 and R3 in the chemical formula 2 as a straight-chain alkyl group or an alkenyl group, and in this case, the precursor including the ligand may have improved vapor pressure, and may be easily formed in a liquid form through improved degrees of freedom, and may also obtain low viscosity characteristics.

[0107] Meanwhile, the above R1 and R3 are each independently a C1-C5 straight-chain alkyl group or alkenyl group, and the above R2 may be a C1-C5 straight-chain alkyl group or alkenyl group.

[0108] In addition, both R1 and R3 are the same and may be a C1-C5 straight-chain, branched or cyclic alkyl group or alkenyl group.

[0109] In addition, all of the above R1 to R3 are the same and may be a C1-C4 straight-chain, branched or cyclic alkyl group or alkenyl group.

[0110] Exemplary structures of such amidinate ligands include one or more selected from the following chemical structures.

[0111]

[0112]

[0113]

[0114]

[0115] Meanwhile, the precursor for forming a thin film including the amidinate ligand may have a central metal atom that is any one of a group 2 to 6 element, a group 13 element, a group 15 element, a transition metal, and a rare earth element.

[0116] As a non-limiting example, the central metal atom may be yttrium (Y), scandium (Sc), or any one of the lanthanide elements.

[0117] In addition, as a non-limiting example, precursors for forming a thin film that can be represented by the above chemical formula 1 include compounds represented by various chemical structures as follows.

[0118] For example, compounds in which L contains a substituted or unsubstituted cyclopentadienyl group include the following compounds.

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127] Additionally, the following compounds can be exemplified as cases where L is the same as AMD.

[0128]

[0129]

[0130]

[0131]

[0132] Additionally, the following compounds can be exemplified when L is an amine group.

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145] The precursor for forming a thin film according to the present invention can be provided in a liquid form at room temperature with low viscosity, high heat resistance, and high volatility by including an amidinate ligand, thereby enabling the formation of a high-quality thin film. In particular, the precursor for forming a thin film can exhibit properties suitable for a thin film formation process, such as a viscosity of 60 cP (25°C) or less.

[0146] In addition, the precursor for forming a thin film of the present invention may additionally include a solvent for dissolving or diluting the precursor compound, taking into consideration the conditions and efficiency of the thin film forming process. The solvent may be C1-C 16 Any one or a mixture of saturated or unsaturated hydrocarbons, ketones, ethers, glymes, esters, tetrahydrofuran, and tertiary amines may be used. The C1-C 16 Examples of saturated or unsaturated hydrocarbons include pentane, cyclohexane, ethylcyclohexane, heptane, octane, toluene, etc., and examples of tertiary amines include dimethylethylamine and triethylamine.

[0147] In particular, depending on the chemical structure, the compound of the precursor for forming a thin film may be in a solid state at room temperature, in which case the compound can be dissolved by including the solvent. That is, when the solvent is included, the solvent is included in an amount capable of dissolving the precursor compound, and it is preferably included in an amount of 1 to 99 wt% based on the total weight of the precursor for forming a thin film.

[0148] Since the precursor, which may or may not contain the above solvent, is vaporizable, it can be supplied into the chamber in the form of a precursor gas. Accordingly, depending on the type of precursor compound, if it exists in a liquid state at room temperature and can be easily vaporized, the thin film formation process can be performed without a separate solvent.

[0149] In this case, the thin film formation process can be performed by any one of 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.

[0150] For example, when the HDP-CVD process is applied, it can be performed under high vacuum and high power compared to the atmospheric pressure chemical vapor deposition process (AP-CVD), low pressure chemical vapor deposition process (LP-CVD), or plasma enhanced chemical vapor deposition process (PE-CVD), so it is possible to form a thin film that is structurally dense and has excellent mechanical properties.

[0151] To this end, the thin film forming method according to the present invention includes a process of forming a thin film on a substrate using the precursor for forming the thin film.

[0152] Specifically, the process of forming a thin film on the substrate may include a process of forming a precursor thin film by depositing a precursor for forming the thin film on the surface of the substrate and a process of reacting the precursor thin film with a reactant.

[0153] In addition, a process of vaporizing the precursor for forming the thin film and transporting it into the chamber for deposition of the precursor may be included.

[0154] In addition, the process of forming a thin film on the substrate may include a process of forming a thin film of a metal, oxide, nitride, oxynitride, or the like by supplying a precursor for forming the thin film to the substrate and applying plasma in the presence of a reactant.

[0155] The process of forming the above thin film can be performed under chamber pressure conditions of 0.1 to 1000 mTorr. In addition, the source power for forming plasma within the chamber is appropriately 500 to 9,000 W, and the bias power is appropriately 0 to 5,000 W. In addition, the bias power may not be applied in some cases.

[0156] Additionally, it is preferable that the process of forming a thin film on the substrate be performed at a temperature range of 150 to 500°C.

[0157] In addition, when supplying the precursor for forming the above thin film, a second metal precursor may be introduced as needed to further improve the electrical characteristics of the finally formed metal film, i.e., the electrostatic capacity or leakage current value. The second metal precursor may optionally further supply a metal precursor including one or more metals (M") selected from magnesium (Mg), strontium (Sr), barium (Ba), lanthanide (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 an alkoxy compound including the metal. For example, when the metal is Si, 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. may be used as the second metal precursor. Can be.

[0158] The supply of the second metal precursor may be performed in the same manner as the supply method of the precursor for forming the thin film, and the second metal precursor may be supplied onto the substrate for forming the thin film together with the precursor, or may be supplied sequentially after the supply of the precursor is completed.

[0159] It is preferable that the precursor and optionally the second metal precursor as described above be maintained at a temperature of 50 to 250°C, more preferably 100 to 200°C, before being supplied into the reaction chamber to contact the substrate for forming the thin film.

[0160] In addition, after the precursor supply step and prior to the supply of the reactant, a process of purging the inside of the reactor with an inert gas such as argon (Ar), nitrogen (N2), or helium (He) may be performed to assist the movement of the precursor and optionally the second metal precursor onto the substrate, to ensure that the inside of the reactor has an appropriate pressure for deposition, and to discharge impurities, etc., existing in the chamber to the outside. At this time, the purging of the inert gas is preferably performed so that the pressure inside the reactor becomes 1 to 5 Torr.

[0161] In addition, any one of nitrogen (N2), ammonia (NH3), hydrazine (N2H4), nitrous oxide (N2O), oxygen (O2), water vapor (H2O), ozone (O3), hydrogen peroxide (H2O2), silane, hydrogen (H), diborane (B2H6), or a mixture thereof may be used as the reactant. When carried out in the presence of an oxidizing gas such as water vapor, oxygen, or ozone, a magnesium oxide thin film may be formed, and when carried out in the presence of a reducing gas such as hydrogen, ammonia, hydrazine, or silane, a thin film of a metal monolayer or metal nitride may be formed. In addition, a metal oxynitride thin film may also be formed by mixing the reactants.

[0162] In addition to plasma treatment, a heat treatment or photo-irradiation treatment process may also be performed. This process provides thermal energy for the deposition of precursors for forming thin films, and can be performed using conventional methods. Preferably, the treatment process is performed so that the temperature of the substrate within the reactor is 100 to 1,000°C, preferably 250 to 400°C, to produce a thin film having the desired physical state and composition at a sufficient growth rate.

[0163] In addition, during the above treatment process, as described above, a process of purging the reactor with an inert gas such as argon (Ar), nitrogen (N2), or helium (He) may be performed in order to help the reactants move onto the substrate, to ensure that the reactor has an appropriate pressure for deposition, and to discharge impurities or byproducts existing in the reactor to the outside.

[0164] As described above, the process of introducing a precursor for forming a thin film, introducing a reactant, and introducing an inert gas is considered one cycle. By repeating this process for one or more cycles, a thin film can be formed.

[0165] In addition, by applying the above thin film formation process, various semiconductor devices including thin films can be manufactured.

[0166] Hereinafter, the effects of the present invention will be explained through examples.

[0167] Example 1: Synthesis of diethyl-ethylamidinate (Et2Et-AMD)

[0168] In a 500 ml Schlenk flask, 132.1 g (0.75 mol) of triethyl ortho-propionate and 74.3 g (1.65 mol) of ethylamine were added, cooled to -30°C, and stirred. At the same temperature, 99.0 g (1.65 mol) of acetic acid was slowly added dropwise, and refluxed at 170°C. After 18 hours, the solvent was removed under reduced pressure, and extraction was performed with 5 N aqueous sodium hydroxide (NaOH) solution and diethylether. After drying over magnesium sulfate, the solvent was removed under reduced pressure, and distillation was performed under reduced pressure to obtain 46.1 g (48%) of a colorless liquid compound. The results of NMR analysis are shown in Fig. 1.

[0169] 1 H NMR (CDCl3, 25°C): 1.13 (m, 9H), 2.20 (q, 2H), 3.17 (m, 4H).

[0170] Purification conditions: 75~78℃ @ 2.4 torr

[0171] The pale yellow liquid left almost no residual mass, remaining at 0% during TGA analysis measured at a temperature rise rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min. This result was confirmed by the TGA analysis results (Fig. 2), which show the percentage of weight loss according to temperature change.

[0172] Example 2: Synthesis of diethyl-n-propyl amidinate (Et2nPr-AMD)

[0173] In a 500 ml Schlenk flask, 122.5 g (0.64 mol) of 1,1,1-triethoxybutane and 58.0 g (1.29 mol) of ethylamine were added, cooled to -30°C, and stirred. At the same temperature, 77.3 g (1.29 mol) of acetic acid was slowly added dropwise, and refluxed at 170°C. After 18 hours, the solvent was removed under reduced pressure, and extraction was performed with a 5 N aqueous sodium hydroxide (NaOH) solution and diethylether. After drying over magnesium sulfate, the solvent was removed under reduced pressure, and distillation was performed under reduced pressure to obtain 36.6 g (40%) of a colorless liquid compound. The results of NMR analysis are shown in Fig. 3.

[0174] 1 H NMR (CDCl3, 25°C): 0.98(t, 3H), 1.15(m, 6H), 1.59(m, 2H), 2.15(m, 2H), 3.22(m, 4H).

[0175] Purification conditions: 82~87℃ @ 0.5 torr

[0176] The pale yellow liquid left almost no residual mass, 0%, during TGA analysis measured at a temperature rise rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min. This result was confirmed by the TGA analysis results (Fig. 4), which show the percentage of weight loss according to temperature change.

[0177] Example 3: Synthesis of dinormal propyl-ethyl amidinate (nPr2Et-AMD)

[0178] In a 500 ml Schlenk flask, 132.1 g (0.75 mol) of triethyl ortho-propionate and 97.5 g (1.65 mol) of n-Propylamine were added, cooled to -30°C, and stirred. At the same temperature, 49.5 g (0.83 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 extraction was performed with 5 N aqueous sodium hydroxide (NaOH) solution and diethylether. After drying over magnesium sulfate, the mixture was filtered, and the solvent was removed under reduced pressure. Distillation under reduced pressure yielded 48.0 g (41%) of a colorless liquid compound. The results of NMR analysis are shown in Fig. 5.

[0179] 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).

[0180] Purification conditions: 80~90℃ @ 0.5 torr

[0181] The pale yellow liquid left almost no residual mass, 0%, during TGA analysis measured at a temperature rise rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min. This result was confirmed by the TGA analysis results (Fig. 6), which show the percentage of weight loss according to temperature change.

[0182] Example 4: Synthesis of bis(ethylcyclopentadienyl)(diethyl-ethyladiene)yttrium [(EtCp)2Y(Et2Et-AMD)]

[0183] To 300 ml of THF, 32.83 g (0.256 mol) of diethyl-ethyl amidinate was added, and after cooling to -78°C, 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, warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-(Et2Et-AMD) solution was slowly added dropwise to a flask containing (EtCp)2YCl at room temperature, 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 purified at 165°C and 40 mTorr to obtain a pale yellow liquid. The yield was 60.1 g (58.3%). The NMR analysis results are shown in Figure 7.

[0184] 1 H NMR (C6D6, 25°C): 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).

[0185] The pale yellow liquid left almost no residual mass, 0%, during TGA analysis measured at a temperature rise rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min. This result was confirmed by the TGA analysis results (Fig. 8), which show the percentage of weight loss according to temperature change.

[0186] A yellow liquid sample was placed in a sealed DSC container and maintained at 40°C for 10 minutes. During DSC analysis, measured at a temperature ramp rate of 10°C / min, a decomposition peak was observed at 377°C. This result was confirmed by the DSC analysis results (Fig. 9), which show changes in thermal energy according to temperature changes.

[0187] A 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 during the viscosity measurement at 12 RPM.

[0188] Example 5: Synthesis of bis(ethylcyclopentadienyl)(diethyl-normal-propylamidinato)yttrium [(EtCp)2Y(Et2nPr-AMD)]

[0189] To 300 ml of THF, 36.43 g (0.256 mol) of diethyl-n-propyl amidinate was added, and after cooling to -78°C, 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, warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-(Et2nPr-AMD) solution was slowly added dropwise to a flask containing Y(EtCp)2Cl at room temperature, 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.

[0190] 1 H NMR (C6D6, 25°C): 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).

[0191] The pale yellow liquid left almost no residual mass, 0%, during TGA analysis measured at a temperature rise rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min. This result was confirmed by the TGA analysis results (Fig. 11), which show the percentage of weight loss according to temperature change.

[0192] A 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 during the viscosity measurement at 20 RPM.

[0193] Example 6: Synthesis of bis(isopropylcyclopentadienyl)(diethyl-ethylamidinato)yttrium [(iPrCp)2Y(Et2Et-AMD)]

[0194] To 300 ml of THF, 32.83 g (0.256 mol) of diethyl-ethyl amidinate was added, and after cooling to -78°C, 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, warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-(Et2Et-AMD) solution was slowly added dropwise to a flask containing (iPrCp)2YCl at room temperature, 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 mTorr to obtain a yellow liquid. The yield was 63.6 g (70.1%). 1 The results of H NMR (Bruker AV400MHz HD) analysis are shown in Figure 12.

[0195] 1 H NMR (C6D6, 25°C): 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).

[0196] The pale yellow liquid left almost no residual mass, 0%, during TGA (TA instrument SDT Q600) analysis measured at a temperature rise rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min.

[0197] Example 7: Synthesis of bis(methylcyclopentadienyl)(diethyl-normal-propylamidinato)yttrium [(MeCp)2Y(Et2nPr-AMD)]

[0198] To 300 ml of THF, 36.43 g (0.256 mol) of diethyl-n-propyl amidinate was added, and after cooling to -78°C, 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, warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-(Et2nPr-AMD) solution was slowly added dropwise to a flask containing (MeCp)2YCl at room temperature, 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 stirred at 170°C and 67 mTorr to obtain a colorless liquid. The yield was 59.11 g (59.4%). 1 The results of H NMR (Bruker AV400MHz HD) analysis are shown in Figure 13.

[0199] 1 H NMR (C6D6, 25°C): 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).

[0200] The colorless liquid left almost no residual mass, 0.9%, during TGA (TA Instruments SDT Q600) analysis measured at a temperature ramp rate of 10°C / min in a nitrogen-flowing atmosphere of 200 ml / min. These results are shown in Figure 14, which shows the TGA analysis results showing the percentage weight loss with temperature change.

[0201] A colorless liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes. During DSC (TA instrument Discovery 25) analysis, a decomposition peak was observed at 410°C at a temperature ramp rate of 10°C / min.

[0202] Example 8: Synthesis of bis(methylcyclopentadienyl)(dinormalpropyl-ethylamidinato)yttrium [(MeCp)2Y(nPr2Et-AMD)]

[0203] To 300 ml of THF, 40.02 g (0.256 mol) of dinormal propyl-ethyl amidinate was added, and after cooling to -78°C, 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, warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-(nPr2Et-AMD) solution was slowly added dropwise to a flask containing (MeCp)2YCl at room temperature, 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 heated at 155°C and 113 mTorr to obtain a yellow liquid. The yield was 60.1 g (58.3%). The NMR (Bruker AV400MHz HD) analysis results are shown in Figure 15.

[0204] 1 H NMR (C6D6, 25°C): 0.87(t, 9H), 1.37(q, 4H), 2.01(q, 2H), 2.12(s,6H), 2.96(q, 4H), 6.0(dt, 8H).

[0205] The yellow liquid left almost no residual mass, 1.6%, during TGA (TA Instruments SDT Q600) analysis measured at a temperature rise rate of 10°C / min in a nitrogen-flowing atmosphere of 200 ml / min. These results are shown in Figure 16, which shows the TGA analysis results showing the percentage weight loss with temperature change.

[0206] Example 9: Synthesis of bis(ethylcyclopentadienyl)(dimethyl-propylamidinato)yttrium [(EtCp)2Y(Me2-nPrAMD)]

[0207] To 300 ml of THF, 29.24 g (0.256 mol) of dimethyl-n-propyl amidinate was added, and after cooling to -78°C, 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, warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-(Me2-nPrAMD) solution was slowly added dropwise to a flask containing (EtCp)2YCl at room temperature, 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 pale pink liquid was heated at 152°C and 44 mTorr to obtain an orange liquid. The yield was 85.0 g (85.5%). 1 The results of H NMR (Bruker AV400MHz HD) analysis are shown in Figure 17.

[0208] 1 H NMR (C6D6, 25°C): 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).

[0209] The orange liquid left virtually no residual mass, at 1%, during TGA (TA Instruments SDT Q600) analysis measured at a temperature ramp rate of 10°C / min in a nitrogen-flowing atmosphere of 200 ml / min. These results are shown in Figure 18, which shows the TGA analysis results showing the percentage weight loss with temperature change.

[0210] A yellow liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes. During DSC analysis (TA instrument Discovery 25) at a temperature ramp rate of 10°C / min, a decomposition peak was observed at 422°C. These results are shown in Figure 19, which is a DSC analysis result showing the change in thermal energy according to temperature change.

[0211] Example 10: Synthesis of bis(ethylcyclopentadienyl)(diethyl-normal-propylamidinato) scandium [(EtCp)2Sc(Et2nPr-AMD)]

[0212] To 300 ml of THF, 47.01 g (0.330 mol) of diethyl-n-propyl amidinate was added, and after cooling to -78°C, 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, warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-(Et2nPr-AMD) solution was slowly added dropwise to a flask containing (EtCp)2ScCl at room temperature, 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 150°C and 28.4 mTorr to obtain a colorless liquid. The yield was 73.33 g (59.6%). 1 The results of H NMR (Bruker AV400MHz HD) analysis are shown in Figure 20.

[0213] 1H NMR (C6D6, 25°C): 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).

[0214] The pale yellow liquid sample retained 1.2% of its residual mass during TGA analysis, measured at a temperature ramp rate of 10°C / min in a nitrogen-flowing atmosphere of 200 ml / min. These results are shown in Figure 21, which shows the TGA analysis results showing the percentage weight loss with temperature change.

[0215] Example 11: Synthesis of bis(isopropylcyclopentadienyl)(diethyl-normal-propylamidinato)cerium [(iPrCp)2Ce(Et2nPr-AMD)]

[0216] In a 500-mL Schlenk flask, 6.13 g (0.256 mol) of NaH and 140 mL of THF were placed, and 11.54 g (0.081 mol) of diethyl-n-propyl amidinate 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 Na-EtCp and Na-(Et2Et-AMD) mixture solution. 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 obtained 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%).

[0217] The dark purple liquid was analyzed by TGA (TA instrument SDT Q600) at a temperature rise rate of 10℃ / min in an atmosphere flowing nitrogen at 200㎖ / min. 1 / 2 The value was 247.4℃, and the residual mass was 1.1% at 350℃, leaving almost no residue. These results are shown in Figure 22, which is a TGA analysis result showing the percentage of weight loss according to temperature change.

[0218] The synthesis of the target compound was confirmed through TGA analysis results showing a single volatilization curve.

[0219] Additionally, a dark purple liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes, and a decomposition peak was observed at 399°C during DSC (TA instrument Discovery 25) analysis measured at a temperature ramp rate of 10°C / min. These results are shown in Figure 23, which is a DSC analysis result showing the change in thermal energy according to temperature change.

[0220] Example 12: Synthesis of bis(ethylcyclopentadienyl)(diethyl-ethylamidinato)gadolinium [(EtCp)2Gd(Et2Et-AMD)]

[0221] In a 500-mL Schlenk flask, 6.13 g (0.256 mol) of NaH and 140 mL of THF were placed, and 11.54 g (0.081 mol) of diethyl-n-propyl amidinate 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 Na-EtCp and Na-(Et2Et-AMD) mixture solution. 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 obtained 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%).

[0222] The yellow liquid was analyzed by TGA (TA instrument SDT Q600) at a temperature rise rate of 10℃ / min in an atmosphere flowing nitrogen at 200㎖ / min. 1 / 2 The value was 224℃, and the residual mass was 2% at 350℃. These results are shown in Figure 24, which is a TGA analysis result showing the weight loss percentage according to temperature change.

[0223] The synthesis of the target compound was confirmed through TGA analysis results showing a single volatilization curve. Furthermore, a pale yellow liquid sample was placed in a sealed DSC container and maintained at 40°C for 10 minutes. During DSC analysis (TA Instruments Discovery 25), a decomposition peak was observed at 412°C at a temperature ramp rate of 10°C / min. These results are depicted in Figure 25, which is a DSC analysis result showing the change in thermal energy according to temperature change.

[0224] Additionally, the pale yellow liquid was analyzed using a viscometer (Brookfield Ametek DV2T viscometer) in a nitrogen atmosphere to measure viscosity, and it was confirmed to have a low viscosity of 31 cP at 25°C.

[0225] Example 13: Synthesis of bis(ethylcyclopentadienyl)(diethyl-ethylamidinato) disprosium [(EtCp)2Dy(Et2Et-AMD)]

[0226] A 500-mL Schlenk flask was charged with 160 mL of THF, 9.54 g (0.0744 mol) of diethyl-ethyl amidinate, and 14.29 g (0.1489 mol) of ethylcyclopentadiene, 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 stirred at room temperature for one hour to prepare a mixture 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 disprosium chloride was added. After stirring at room temperature for three hours, the mixture was evaporated under vacuum, and the obtained 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%).

[0227] The light green liquid was analyzed by TGA (TA instrument SDT Q600) at a temperature rise rate of 10℃ / min in an atmosphere flowing nitrogen at 200㎖ / min.1 / 2 The value was 225.8℃, and the residual mass was 1.58% at 350℃, leaving almost no residue. These results are shown in Figure 26, which is a TGA analysis result showing the percentage of weight loss according to temperature change.

[0228] The synthesis of the target compound was confirmed through TGA analysis results showing a single volatilization curve. Furthermore, a pale green liquid sample was placed in a sealed DSC container and maintained at 40°C for 10 minutes. During DSC analysis (TA Instruments Discovery 25), a decomposition peak was observed at 418°C at a temperature ramp rate of 10°C / min. These results are depicted in Figure 27, which is a DSC analysis result showing the change in thermal energy with temperature change.

[0229] Additionally, the light green liquid was analyzed with a viscometer (Brookfield Ametek DV2T viscometer) in a nitrogen atmosphere to measure viscosity, and it was confirmed to have a low viscosity of 38 cP at 25°C.

[0230] Example 14: Synthesis of bis(ethylcyclopentadienyl)(diethyl-ethylamidinato)lutetium [(EtCp)2Lu(Et2Et-AMD)]

[0231] A 500-mL Schlenk flask was charged with 160 mL of THF, 9.12 g (0.0711 mol) of diethyl-ethyl amidinate, and 13.39 g (0.1422 mol) of ethylcyclopentadiene, 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 stirred at room temperature for one hour to prepare a mixture 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 three hours, the mixture was evaporated under vacuum, and the obtained 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 H NMR analysis results are as shown in Figure 28, and the following characteristic peaks were obtained.

[0232] 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)

[0233] Additionally, the orange liquid was analyzed by TGA (TA instrument SDT Q600) at a temperature rise rate of 10℃ / min in an atmosphere flowing nitrogen at 200㎖ / min. 1 / 2 The value was 223℃, and the residual mass was 1.4% at 350℃, leaving almost no residue. These results are shown in Figure 29, which is a TGA analysis result showing the percentage of weight loss according to temperature change.

[0234] Additionally, an orange liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes, and a decomposition peak was observed at 455°C during DSC analysis (TA instrument Discovery 25) measured at a temperature ramp rate of 10°C / min. These results are shown in Figure 30, which is a DSC analysis result showing the change in heat energy according to temperature change.

[0235] Additionally, the orange liquid was analyzed with a viscometer (Brookfield Ametek DV2T viscometer) in a nitrogen atmosphere to measure viscosity, and it was confirmed to have a low viscosity of 38 cP at 25°C.

[0236] Example 15: Synthesis of tris(diethyl-normal-propyladiene)yttrium [Y(Et2nPr-AMD)3]

[0237] To 300 ml of THF, 109.28 g (0.768 mol) of diethyl-n-propyl amidinate was added, and after cooling to -78°C, 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, warmed to room temperature, and stirred at room temperature for an additional 2 hours. The prepared Li-(Et2nPr-AMD) solution was slowly added dropwise to a flask containing YCl3 at -78°C 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. The resulting red liquid was purified at 184°C and 31 mTorr to obtain a pale yellow liquid. The yield was 107.5 g (81.9%). The NMR analysis results are shown in Figure 31.

[0238] 1 H NMR (C6D6, 25°C): 0.87(t, 9H), 1.32(t, 18H), 1.52(q, 6H), 2.21(q,6H), 3.24(q, 12H)

[0239] The pale yellow liquid left almost no residual mass, 0.75%, during TGA analysis measured at a temperature rise rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min. This result was confirmed by the TGA analysis results (Fig. 32), which show the percentage of weight loss according to temperature change.

[0240] Example 16: Synthesis of tris-(diethyl-n-propylamidinato)terbium [Tb(Et2nPr-AMD)3]

[0241] Into a 500-mL Schlenk flask, add 10.0 g (0.0377 mol) of TbCl3 and 50 ml of THF, and stir at room temperature for 4 hours. Into a 250-mL Schlenk flask, add 50 ml of THF and 16.1 g (0.114 mol) of diethyl-n-propyl amidinate, cool to -78°C, and slowly add 47.5 ml (0.119 mol) of n-BuLi-hexane solution (2.5 M) dropwise, and stir at room temperature for 2 hours to prepare Li-(Et2nPr-AMD). The prepared Li-(Et2nPr-AMD) solution was added dropwise to a flask containing 10 g (0.0377 mol) of TbCl3 at 0°C, and stirred at room temperature for 6 hours. The mixture was filtered, the solvent and volatiles were evaporated under vacuum, and distilled at 220°C and 138 mTorr to obtain a yellow liquid. The yield was 11.0 g (50.1%).

[0242] The yellow liquid left almost no residual mass, 1.18%, during TGA (TA Instruments SDT Q600) analysis measured at a temperature rise rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min. This result was confirmed from the TGA analysis results showing the weight loss percentage according to temperature change in Fig. 33.

[0243] Additionally, a yellow liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes, and a decomposition peak was observed at 417°C during DSC analysis (TA instrument Discovery 25) measured at a temperature ramp rate of 10°C / min. This result was confirmed from the DSC analysis results showing the change in thermal energy according to the temperature change in Fig. 34.

[0244] Example 17: Synthesis of tris-(diethyl-n-propylamidinato)diceprosium [Dy(Et2nPr-AMD)3]

[0245] Into a 500-mL Schlenk flask, add 10.0 g (0.0372 mol) of DyCl3 and 50 ml of THF, and stir at room temperature for 4 hours. Into a 250-mL Schlenk flask, add 50 ml of THF and 15.9 g (0.112 mol) of diethyl-n-propylamidinate, cool to -78°C, and slowly add 46.9 ml (0.117 mol) of n-BuLi-hexane solution (2.5 M) dropwise, and stir at room temperature for 2 hours to prepare Li-(Et2nPr-AMD). The prepared Li-(Et2nPr-AMD) solution was added dropwise to a flask containing 10 g (0.0372 mol) of DyCl3 at 0°C, and stirred at room temperature for 6 hours. The mixture was filtered, the solvent and volatiles were evaporated under vacuum, and distilled at 220°C and 90 mTorr to obtain a yellow liquid. The yield was 13.8 g (69%).

[0246] The yellow liquid left almost no residual mass, 1.59%, during TGA (TA Instruments SDT Q600) analysis measured at a temperature rise rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min. This result was confirmed from the TGA analysis results showing the weight loss percentage according to temperature change in Fig. 35.

[0247] Additionally, a yellow liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes, and a decomposition peak was observed at 487°C during DSC (TA instrument Discovery 25) analysis measured at a temperature ramp rate of 10°C / min. This result was confirmed from the DSC analysis results showing the change in thermal energy according to the temperature change in Fig. 36.

[0248] Example 18: Synthesis of tris-(diethyl-n-propylamidinato)erbium [Er(Et2nPr-AMD)3]

[0249] Into a 500-mL Schlenk flask, 10.0 g (0.0365 mol) of ErCl3 and 50 ml of THF were added, and the mixture was stirred at room temperature for 4 hours. Into a 250-mL Schlenk flask, 50 ml of THF and 15.6 g (0.110 mol) of diethyl-n-propylamidinate were added, and after cooling to -78°C, 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 prepare Li-(Et2nPr-AMD). The prepared Li-(Et2nPr-AMD) solution was added dropwise to a flask containing 10 g (0.0365 mol) of ErCl3 at 0°C, and the mixture was stirred at room temperature for 6 hours. The mixture was filtered, the solvent and volatiles were evaporated under vacuum, and distilled at 220°C and 80 mTorr to obtain an orange liquid. The yield was 14 g (72%).

[0250] The orange liquid left almost no residual mass, 1.52%, during TGA (TA Instruments SDT Q600) analysis measured at a temperature rise rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min. This result was confirmed by the TGA analysis results showing the weight loss percentage according to temperature change in Fig. 37.

[0251] Additionally, an orange liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes, and a decomposition peak was observed at 466°C during DSC analysis (TA instrument Discovery 25) measured at a temperature ramp rate of 10°C / min. This result was confirmed from the DSC analysis results showing the change in thermal energy according to the temperature change in Fig. 38.

[0252] In addition, to check the viscosity of the orange liquid, a sample was placed in the measuring container of a rotational viscometer (Brookfield LVD2T) and the viscosity was measured using a low-viscosity spindle at 25°C, and it was confirmed to be 77.1 cPs.

[0253] Example 19: Synthesis of tris-(diethyl-n-propylamidinato)ytterbium [Yb(Et2nPr-AMD)3]

[0254] Into a 500-mL Schlenk flask, 10.0 g (0.0358 mol) of YbCl3 and 50 ml of THF were added, and the mixture was stirred at room temperature for 4 hours. Into a 250-mL Schlenk flask, 50 ml of THF and 15.3 g (0.107 mol) of diethyl-n-propylamidinate were added, and after cooling to -78°C, 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 prepare Li-(Et2nPr-AMD). The prepared Li-(Et2nPr-AMD) solution was added dropwise to a flask containing 10 g (0.0358 mol) of YbCl3 at 0°C, and the mixture was stirred at room temperature for 6 hours. The mixture was filtered, the solvent and volatiles were evaporated under vacuum, and distilled at 220°C and 68 mTorr to obtain a yellow liquid. The yield was 14 g (70%).

[0255] The yellow liquid left almost no residual mass, 1.68%, during TGA (TA Instruments SDT Q600) analysis measured at a temperature rise rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min. This result was confirmed by the TGA analysis results showing the weight loss percentage according to temperature change in Fig. 39.

[0256] In addition, to check the viscosity of the yellow liquid, a sample was placed in the measuring container of a rotational viscometer (Brookfield LVD2T) and the viscosity was measured with a low-viscosity spindle at 25°C, and was shown at 66.2 cPs.

[0257] Example 20: Synthesis of tris-(diethyl-n-propylamidinato)lutetium [Lu(Et2nPr-AMD)3]

[0258] Into a 500-mL Schlenk flask, 10.0 g (0.0355 mol) of LuCl3 and 50 ml of THF were added, and the mixture was stirred at room temperature for 4 hours. Into a 250-mL Schlenk flask, 50 ml of THF and 15.2 g (0.107 mol) of diethyl-n-propylamidinate were added, and after cooling to -78°C, 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 prepare Li-(Et2nPr-AMD). The prepared Li-(Et2nPr-AMD) solution was added dropwise to a flask containing 10 g (0.0355 mol) of LuCl3 at 0°C, and the mixture was stirred at room temperature for 6 hours. The mixture was filtered, the solvent and volatiles were evaporated under vacuum, and distilled at 220°C and 54 mTorr to obtain an orange liquid. The yield was 16.2 g (75.8%). 1 The results of H NMR analysis are as shown in Figure 40.

[0259] 1 H NMR (C6D6, 25°C): 0.88(t, 9H), 1.30(t, 18H), 1.51(q, 6H), 2.21(q, 6H), 3.28(q, 12H).

[0260] The orange liquid left almost no residual mass, 0.95%, during TGA (TA Instruments SDT Q600) analysis measured at a temperature ramp rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min. This result was confirmed by the TGA analysis results showing the weight loss percentage according to temperature change in Fig. 41.

[0261] Additionally, an orange liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes, and a decomposition peak was observed at 442°C during DSC analysis (TA instrument Discovery 25) measured at a temperature ramp rate of 10°C / min. This result was confirmed from the DSC analysis results showing the change in thermal energy according to the temperature change in Fig. 42.

[0262] Example 21: Preparation of (CH2CH2CH2N-C(CH2CH3)=N-CH2CH2CH3)2Hf(DMA)2

[0263] In a 250 mL Schlenk flask under a nitrogen atmosphere, 2.8 g (0.0080 mol) of tetrakis(dimethylamino)hafnium (Hf(NMe2)4) and 50 mL of n-hexane were charged, and 2.5 g (0.0160 mol) of (E)-N,N'-dipropylpropionimidamide was slowly added dropwise at room temperature, followed by stirring at room temperature for 14 hours. After the reaction was completed, the obtained reaction solution was reduced in pressure to remove the solvent and volatile by-products. The removed remaining liquid was purified at 126.6°C (63.4 mTorr) to obtain 1 g (yield 21.7%) of pale yellow viscous liquid compound 1. 1 The results of H NMR analysis are as shown in Figure 43.

[0264] 1 H NMR (C6D6, 25°C): 3.326(s, 12H), 3.23(t, 8H), 2.00(q, 4H), 1.64(m, 8H), 0.96(t, 12H), 0.93(t, 6H).

[0265] The pale yellow liquid left almost no residual mass, 0.95%, during TGA (TA Instruments SDT Q600) analysis measured at a temperature rise rate of 10°C / min in a nitrogen flowing atmosphere of 200 ml / min. This result was confirmed by the TGA analysis results showing the weight loss percentage according to temperature change in Fig. 44(a).

[0266] Additionally, an orange liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes, and a decomposition peak was observed at 351°C during DSC (TA instrument Discovery 25) analysis measured at a temperature ramp rate of 10°C / min (Fig. 44(b)).

[0267] Example 22: Preparation of (CH2CH2N-C(CH2CH2CH3)=N-CH2CH3)2Hf(DMA)2

[0268] In a 250 mL Schlenk flask 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, and 2.5 g (0.0176 mol) of (E)-N,N'-diethylprobutyrimidamide was slowly added dropwise at room temperature, followed by stirring at room temperature for 14 hours. After the reaction was completed, the obtained reaction solution was reduced in pressure to remove the solvent and volatile by-products. The removed remaining liquid was purified at 117.2°C (54.3 mTorr) to obtain 2 g (yield 41.7%) of pale yellow liquid compound 3. 1 The results of H NMR analysis are as shown in Figure 45.

[0269] 1 H NMR (C6D6, 25°C): 3.345(s, 12H), 3.31(q, 8H), 2.02(m, 4H), 1.44(m, 4H), 1.19(t, 12H), 0.83(t, 6H).

[0270] The pale yellow liquid left almost no residual mass, 0.53%, during TGA (TA Instruments SDT Q600) analysis measured at a temperature rise rate of 10°C / min in a nitrogen flowing atmosphere of 200 ml / min. This result was confirmed by the TGA analysis results showing the weight loss percentage according to temperature change in Fig. 46(a).

[0271] Additionally, a light yellow sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes, and a decomposition peak was observed at 330°C during DSC (TA instrument Discovery 25) analysis measured at a temperature ramp rate of 10°C / min (Fig. 46(b)).

[0272] Example 23: Preparation of (CH2CH2N-C(CH2CH2CH3)=N- CH2CH3)2Hf(EMA)2

[0273] In a 250 mL Schlenk flask 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, and 2.5 g (0.0176 mol) of (E)-N,N'-diethylprobutyrimidamide was slowly added dropwise at room temperature, followed by stirring at room temperature for 14 hours. After the reaction was completed, the obtained reaction solution was reduced in pressure to remove the solvent and volatile by-products. The remaining liquid was purified at 123.4°C (25.3 mTorr) to obtain 2 g (yield 39.2%) of pale yellow liquid compound 4. 1 The H NMR analysis results are as shown in Figure 47.

[0274] 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).

[0275] The pale yellow liquid left almost no residual mass, 0.95%, during TGA (TA Instruments SDT Q600) analysis measured at a temperature rise rate of 10°C / min in a nitrogen flowing atmosphere of 200 ml / min. This result was confirmed by the TGA analysis results showing the weight loss percentage according to temperature change in Fig. 48(a).

[0276] Additionally, a light yellow liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes, and a decomposition peak was observed at 339°C during DSC (TA instrument Discovery 25) analysis measured at a temperature ramp rate of 10°C / min (Fig. 48(b)).

[0277] Example 24: Preparation of (CH2CH2N -C(CH2CH2CH3)=N- CH2CH3)2Zr(DMA)2

[0278] In a 250 ml Schlenk flask under a nitrogen atmosphere, 4 g (0.0150 mol) of tetrakis(dimethylamino)zirconium (Zr(NMe2)4) and 50 ml of n-hexane were charged, and 4.3 g (0.0300 mol) of (E)-N,N'-diethylpropionitrimidamide was slowly added dropwise at room temperature, followed by stirring at room temperature for 14 hours. After the reaction was completed, the reaction solution was reduced in pressure to remove the solvent and volatile by-products. The remaining liquid was purified at 116.2°C (67.8 mTorr) to obtain 2.9 g (yield 42.0%) of pale yellow liquid compound 5. 1 The H NMR analysis results are as shown in Figure 49.

[0279] 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)

[0280] The pale yellow liquid left almost no residual mass, 0.95%, during TGA (TA Instruments SDT Q600) analysis measured at a temperature rise rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min. This result was confirmed from the TGA analysis results showing the weight loss percentage according to temperature change in Fig. 50(a).

[0281] Additionally, a light yellow liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes, and a decomposition peak was observed at 304°C during DSC (TA instrument Discovery 25) analysis measured at a temperature ramp rate of 10°C / min (Fig. 50(b)).

[0282] Example 25: Preparation of (2-ethyl-N,N-diethylamidinato)bis(dimethylamino)borane [(Et2Et-AMD)B(DMA)2]

[0283] In reaction vessel 1, 5.9 g (0.04 mol) of tris(dimethylamino)borane [TDMAB] was diluted with 30 ml of hexane, cooled to a cryogenic temperature (approximately -20°C), 2 ml (0.02 mol) of tribromoboron (BBr3) was added, and stirred at room temperature for about 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, cooled to a cryogenic temperature (approximately -20°C), and 24.9 ml (0.06 mol) of 2.5 M n-butyl lithium (nBuLi) was slowly added, and stirred at room temperature for about 6 hours. After re-cooling reaction vessel 1 to a cryogenic temperature (approximately -20°C), the solution from reaction vessel 2 was slowly transferred and added, and stirred at room temperature for approximately 12 hours. The reactant was filtered, and the solvent in the resulting filtrate was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure to obtain 8.5 g (yield: 61%). 1 The H NMR analysis results are as shown in Figure 51. 11 The B NMR analysis results are as shown in Figure 52.

[0284] 1 H NMR (C6D6, 25°C): 0.96 (t, 3H), 1.36(t, 6H), 2.13(q, 2H), 2.44(s, 12H), 3.49(q, 4H).

[0285] 11 B-NMR: 28.09 ppm.

[0286] Example 26: Preparation of (2-methyl-N,N-diisopropylamidinato)bis(dimethylamino)borane [(iPr2Me-AMD)B(DMA)2]

[0287] In reaction vessel 1, 5.9 g (0.04 mol) of tris(dimethylamino)borane [TDMAB] was diluted with 20 ml of hexane, cooled to a cryogenic temperature (approximately -20°C), 2 ml (0.02 mol) of tribromoboron (BBr3) was added, and 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, cooled to a cryogenic temperature (approximately -20°C), and 42.8 ml (0.06 mol) of 1.6 M methyl lithium (MeLi) was slowly added, and stirred at room temperature for approximately 6 hours. After re-cooling reaction vessel 1 to a cryogenic temperature (approximately -20°C), the solution in reaction vessel 2 was slowly transferred and added, and stirred at room temperature for approximately 12 hours. The reactant was filtered, and the solvent of the obtained filtrate was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [82.5°C @ 1 torr] to obtain 7.5 g (yield: 50%) of a colorless liquid. 1 The H NMR analysis results are as shown in Figure 53. 11 The B NMR analysis results are as shown in Figure 54.

[0288] 1 H NMR (C6D6, 25°C): 1.31(d, 12H), 1.60(s, 3H), 2.43(s, 12H), 4.05(m, 2H).

[0289] 11 B-NMR: 28.07 ppm.

[0290] Example 27: Preparation of (2-ethyl-N,N-diethylamidinato)(N,N-dimethylethylenediamino)borane [(Et2Et-AMD)B(DMA-EDA)]

[0291] Triethylamine (79 ml, 0.56 mol) was diluted with hexane (200 ml) and cooled to low temperature (approximately 0°C). A solution of tribromoboron (BBr3) (26.9 ml, 0.28 mol) diluted with hexane (40 ml) was added and stirred at room temperature for approximately 2 hours. N,N-dimethylethylenediamine (N,N-dimethylethylenediamine) (25 g, 0.28 mol) diluted with hexane (100 ml) was added and stirred while heating for approximately 3 hours. The reactant was filtered, and the solvent of the obtained 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.

[0292] 1 H NMR (C6D6, 25°C): 2.49 (s, 6H,) 2.76 (s, 4H).

[0293] 11 B-NMR: 26.32 ppm.

[0294] In reaction vessel 2, 3.62 g (0.02 mol) of 2-ethyl-N,N-diethylamidinate was diluted with 30 ml of hexane, cooled to an extremely low temperature (approximately -20°C), and 11.3 ml (0.02 mol) of 2.5 M n-butyl lithium (nBuLi) was slowly added and stirred at room temperature for approximately 6 hours. In reaction vessel 1, 5 g (0.02 mol) of 2-bromo-1,3-dimethyl-1,3,2-diazaborolane was diluted with 10 ml of hexane and cooled to a cryogenic temperature (approximately -20°C). The solution in reaction vessel 2 was slowly transferred and added thereto, followed by stirring at room temperature for approximately 12 hours. The reactant was filtered, and the solvent of the obtained filtrate was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [63.3°C@1 torr] to obtain 3.6 g (yield: 60%) of a colorless liquid. 1 The H NMR analysis results are as shown in Figure 55. 11 The B NMR analysis results are as shown in Figure 56.

[0295] 1 H NMR (C6D6, 25°C): 1.01(t, 3H), 1.35(t, 6H), 2.19(q, 2H), 2.42(s, 6H), 2.88 (s, 4H), 3.52(q, 4H).

[0296] 11 B-NMR: 28.31 ppm

[0297] Example 28: Preparation of (N-ethyl-2-isobutyl-N-propylamidinato)bis(dimethylamino)borane [(EtPrisoBu-AMD)B(DMA)2]

[0298] In reaction vessel 1, 5.9 g (0.04 mol) of tris(dimethylamino)borane [tris(dimethylamino)borane, TDMAB] was diluted with 15 ml of hexane, cooled to an extremely low temperature (approximately -20°C), and 2 ml (0.02 mol) of tribromoboron (BBr3) was added and 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 and cooled to a cryogenic temperature (approximately -20°C). 24.9 ml (0.06 mol) of 2.5 M n-butyl lithium (nBuLi) was slowly added and stirred at room temperature for approximately 6 hours. Reaction vessel 1 was re-cooled to a cryogenic temperature (approximately -20°C), and the solution from reaction vessel 2 was slowly transferred and added and stirred at room temperature for approximately 12 hours. The reactant was filtered, and the solvent of the obtained filtrate was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [83.7℃ @0.1torr] to obtain 12.4 g (yield: 74%) of a colorless liquid. 1 The H NMR analysis results are as shown in Figure 57. 11 The B NMR analysis results are as shown in Figure 58.

[0299] 1 H NMR (C6D6, 25°C): 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).

[0300] 11 B-NMR: 28.25 ppm.

[0301] Through these experimental results, it was confirmed that a liquid precursor having sufficient vapor pressure and thermal stability to be used as a semiconductor precursor in a structure applying the novel amidinate ligand according to the present invention could be obtained, and in particular, the viscosity characteristics of the precursor were greatly improved.

[0302] While the present invention has been described with reference to preferred embodiments as described above, it is not limited to the above-described embodiments, and various modifications and variations are possible by those skilled in the art without departing from the spirit of the invention. Such modifications and variations are deemed to fall within the scope of the present invention and the appended claims.

Claims

1. A precursor for forming a thin film comprising a compound represented by the following chemical formula 1, A precursor for forming a thin film, characterized in that the precursor for forming a thin film is 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 a central metal atom, which is any one of 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 the AMD, and when different from the AMD, is any one of a substituted or unsubstituted cyclopentadienyl group, amine, alcohol, alkyl, aryl, amino amine, alkoxy amine, amino alcohol, alkoxy alcohol, imido, diamine, dialcohol, formidinate, guanidinate, beta-diketonate, ketoiminate, amide, and halide. n is an integer from 0 to 5, m is an integer from 1 to 6.

2. In claim 1, A precursor for forming a thin film, characterized in that the above AMD is a ligand represented by the following chemical formula 2. [Chemical Formula 2] In the above chemical formula 2, R1 and R3 are each independently a C1-C5 straight-chain, branched or cyclic alkyl group or alkenyl group, R2 is a hydrogen atom or a C1-C5 straight-chain, branched or cyclic alkyl or alkenyl group.

3. In claim 2, A precursor for forming a thin film, characterized in that in the above chemical formula 2, R2 is a C2-C5 straight-chain, branched or cyclic alkyl group or alkenyl group.

4. In claim 2, A precursor for forming a thin film, characterized in that in the above chemical formula 2, R1 and R3 are each independently a C2-C5 straight-chain, branched or cyclic alkyl group or alkenyl group, and R2 is a C2-C5 straight-chain, branched or cyclic alkyl group or alkenyl group.

5. In claim 2, A precursor for forming a thin film, characterized in that in the above chemical formula 2, R1 and R3 are methyl groups.

6. In claim 2, A precursor for forming a thin film, characterized in that in the above chemical formula 2, R2 is an isopropyl group.

7. In claim 2, A precursor for forming a thin film, characterized in that in the above chemical formula 2, R1 and R3 are each independently a straight-chain alkyl group or alkenyl group of C1-C5.

8. In claim 2, A precursor for forming a thin film, characterized in that in the above chemical formula 2, R1 and R3 are each independently a C1-C5 straight-chain alkyl group or alkenyl group, and R2 is a C1-C5 straight-chain alkyl group or alkenyl group.

9. In claim 2, A precursor for forming a thin film, characterized in that in the above chemical formula 2, R1 and R3 are both the same and are a C1-C5 straight-chain, branched or cyclic alkyl group or alkenyl group.

10. In claim 2, A precursor for forming a thin film, characterized in that in the above chemical formula 2, R1 to R3 are all the same and are a C1-C4 straight-chain, branched or cyclic alkyl group or alkenyl group.

11. In claim 2, An amidinate ligand characterized in that the amidinate ligand is one or more selected from the following chemical structures.

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

13. In claim 1, A precursor for forming a thin film, characterized in that the compound represented by the above chemical formula 1 is one or more selected from the following chemical structures.

14. In claim 1, A precursor for forming a thin film, characterized in that the compound represented by the above chemical formula 1 is one or more selected from the following chemical structures.

15. In claim 1, A precursor for forming a thin film, characterized in that the compound represented by the above chemical formula 1 is one or more selected from the following chemical structures.

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