Method for preparing organometallic compound

Abstract

The present invention relates to a method for preparing an organometallic compound for a vapor deposition precursor with high yield, the method comprising the steps of: reacting a compound containing a halogen element with a Grignard reagent; and reacting a substituted or unsubstituted aromatic ring.

Description

Method for preparing organometallic compounds

[0001] The present invention relates to a method for manufacturing an organometallic compound that can be used as a vapor deposition precursor capable of thin film deposition through vapor deposition.

[0002] Recently, as the integration density of semiconductor devices increases rapidly, there is a need for technology in semiconductor wiring processes that can uniformly deposit thin films at high aspect ratios and stack metal thin films of uniform thickness regardless of structure.

[0003] Improvements in deposition process technology and precursor compounds are required for the fabrication of such metal thin films.

[0004] To this end, the application of atomic layer deposition (ALD) is rapidly expanding in terms of the development of deposition process technology.

[0005] Atomic layer deposition is a self-limiting reaction occurring on a surface, and thin films can be realized through deposition at the atomic layer level. Due to its excellent step coverage, thin films of uniform thickness can be deposited over large areas and complex three-dimensional structures.

[0006] With the expansion of atomic layer deposition applications, there is a growing need for various organometallic compounds that can be optimized and used as precursors for atomic layer deposition.

[0007] The gate oxide (=gate dielectric) used in the gate structure of MOSFETs (metal-oxide-semiconductor field effect transistors), which are the core of current electronic devices, is based on silicon oxide.

[0008] However, as devices have recently become smaller and more highly integrated, problems such as increased leakage current due to thin oxide films and the formation of gate depletion layers are occurring.

[0009] Devices utilizing conventional SiO2 as the gate dielectric are already showing limitations in low-power devices, and even in high-performance devices, significant heat generation due to leakage current remains a problem. To address these issues, many attempts are being made to use new oxides with high dielectric constants.

[0010] Accordingly, high dielectric constant, thermodynamic stability, high temperature stability, thin film uniformity, interface characteristics with silicon substrates, compatibility with MOS process technology, and reliability are required as conditions for gate dielectrics to replace SiO2; oxide films containing Zr, Ti, or Hf (such as ZrO2, TiO2, and HfO2) are being considered as materials that reflect these aspects.

[0011] As the demand for new gate dielectrics (oxide films containing Zr, Ti, or Hf) increases, the development of precursors for their manufacture is actively underway.

[0012] In particular, there is a demand for a manufacturing method that can synthesize precursors at a low cost and with a higher reaction yield compared to existing precursor manufacturing methods.

[0013] [Prior Art Literature]

[0014] [Patent Literature]

[0015] (Patent Document 1) Republic of Korea Published Patent Application No. 2022-0033590

[0016] Accordingly, the present invention aims to provide a method for manufacturing an organometallic compound.

[0017] In particular, the reaction yield of the organometallic compound can be significantly improved and manufacturing costs reduced through the above-described method for manufacturing the organometallic compound. That is, organometallic compounds can be conveniently manufactured at a low cost by using only a single reactor and introducing the reactants.

[0018] In addition, the method for manufacturing the organometallic compound above generates a liquid byproduct, which can reduce the risk associated with the generation of gaseous byproducts (e.g., butane gas) in conventional methods for manufacturing organometallic compounds.

[0019] However, the problems that this invention seeks to solve are not limited to those mentioned above, and other unmentioned problems will be clearly understood by those skilled in the art from the description below.

[0020] One aspect of the present invention comprises: a first step of reacting a compound of Formula 1 with a compound of Formula 2; and

[0021] A second step of synthesizing a compound of Formula 4 by reacting the product of the reaction in the first step with a compound of Formula 3; comprising

[0022] A method for manufacturing an organometallic compound is provided.

[0023]

[0024] [Chemical Formula 1]

[0025] M(X1)4

[0026] In the above chemical formula 1,

[0027] M is a group 4 element, and

[0028] X1 is a halogen atom.

[0029]

[0030] [Chemical Formula 2]

[0031] R1-Mg-X2

[0032]

[0033] In the above chemical formula 2,

[0034] R1 is phenyl; benzyl; o-toluidine that is unsubstituted or substituted with one or more alkyl groups having 1 to 3 carbon atoms; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof,

[0035] X2 is a halogen atom.

[0036]

[0037] [Chemical Formula 3]

[0038] HNR2R3

[0039]

[0040] In the above chemical formula 3,

[0041] R2 and R3 are each independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof.

[0042]

[0043] [Chemical Formula 4]

[0044] M(NR4R5)4

[0045]

[0046] In the above chemical formula 4,

[0047] M is a group 4 element, and

[0048] R4 and R5 are each independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof.

[0049] The method for preparing the above organometallic compound may further include a third step of reacting the compound of Formula 4 with a substituted or unsubstituted aromatic ring.

[0050] In the method for preparing the above organometallic compound, the substituted or unsubstituted aromatic ring may be any one selected from the group consisting of substituted or unsubstituted pyrrole and substituted or unsubstituted cyclopentadiene.

[0051] In the method for preparing the above organometallic compound, the substituted or unsubstituted pyrrole is represented by Chemical Formula 5, and

[0052] The above substituted or unsubstituted cyclopentadiene can be represented by Chemical Formula 6.

[0053]

[0054] [Chemical Formula 5]

[0055]

[0056]

[0057] In the above chemical formula 5,

[0058] R6 to R9 are each independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof.

[0059]

[0060] [Chemical Formula 6]

[0061]

[0062]

[0063] In the above chemical formula 6,

[0064] R 10 to R 14 Each is independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; a linear or branched alkyl amine having 3 to 7 carbon atoms; or a combination thereof.

[0065] In the method for preparing the above organometallic compound, the substituted or unsubstituted cyclopentadiene may be one or more selected from the group consisting of cyclopentadiene, N-methyl 2-cyclopentadienyl propylamine, and 2-(cyclopentadienyl)-N,2-dimethylpropanamine.

[0066] In a method for preparing the above organometallic compound, the compound of Formula 1, the compound of Formula 2, and the substituted or unsubstituted aromatic ring are sequentially injected into a reactor, or

[0067] The compound of Formula 1, the compound of Formula 2, and the substituted or unsubstituted aromatic ring can be simultaneously injected into the reactor.

[0068] In the method for preparing the above organometallic compound, the organometallic compound may be one or more selected from the group consisting of the compound represented by Formula 7, the compound represented by Formula 8, and the compound represented by Formula 9.

[0069]

[0070] [Chemical Formula 7]

[0071]

[0072]

[0073] In the above chemical formula 7,

[0074] M is a group 4 element, and

[0075] R 15 to R 25 Each is independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof.

[0076]

[0077] [Chemical Formula 8]

[0078]

[0079]

[0080] In the above chemical formula 8,

[0081] M is a group 4 element, and

[0082] R 26 to R 33 Each is independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof, and

[0083] Me is a methyl group.

[0084]

[0085] [Chemical Formula 9]

[0086]

[0087]

[0088] In the above chemical formula 9,

[0089] M is a group 4 element, and

[0090] R 34 to R 43 Each is independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof.

[0091] In the method for manufacturing the above organometallic compound, the organometallic compound may be a vapor deposition precursor.

[0092] The method for manufacturing an organometallic compound according to the present invention has the effect of improving the reaction yield of the organometallic compound, lowering manufacturing costs, and improving stability.

[0093] In addition, a thin film produced by a method for producing a thin film using an organometallic compound produced by the method for producing an organometallic compound of the present invention as a vapor deposition precursor has excellent physical properties, and said thin film can be used in various electronic devices, particularly semiconductors, displays, solar cells, etc.

[0094] Figure 1 is a flowchart showing each chemical reaction step of the method for preparing ZrCp(NMe2)3(ZrCp[N(CH3)2]3) of Example 1.

[0095] The operation and effects of the invention will be described in more detail below through specific embodiments. However, these embodiments are merely examples of the invention and do not define the scope of the invention.

[0096] Prior to this, terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0097] Therefore, it should be understood that the configuration of the embodiments described in this specification is merely one of the most preferred embodiments of the present invention and does not represent all of the technical ideas of the present invention, and that various equivalents and modifications that can replace them may exist at the time of filing this application.

[0098] In this specification, singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “comprising,” “comprising,” or “having” are intended to specify the existence of the implemented features, numbers, steps, components, or combinations thereof, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0099] In the present specification, "a to b" and "a~b" indicating numerical ranges, "to" and "~" are defined as ≥ a and ≤ b.

[0100]

[0101] A method for preparing an organometallic compound according to one aspect of the present invention may include: a first step of reacting a compound of Formula 1 with a compound of Formula 2; and a second step of synthesizing a compound of Formula 4 by reacting the product of the reaction in the first step with a compound of Formula 3.

[0102]

[0103] [Chemical Formula 1]

[0104] M(X1)4

[0105]

[0106] In the above chemical formula 1,

[0107] M is a group 4 element, and

[0108] X1 is a halogen atom.

[0109]

[0110] [Chemical Formula 2]

[0111] R1-Mg-X2

[0112]

[0113] In the above chemical formula 2,

[0114] R1 is phenyl; benzyl; o-toluidine that is unsubstituted or substituted with one or more alkyl groups having 1 to 3 carbon atoms; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof,

[0115] X2 is a halogen atom.

[0116]

[0117] [Chemical Formula 3]

[0118] HNR2R3

[0119]

[0120] In the above chemical formula 3,

[0121] R2 and R3 are each independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof.

[0122]

[0123] [Chemical Formula 4]

[0124] M(NR4R5)4

[0125]

[0126] In the above chemical formula 4,

[0127] M is a group 4 element, and

[0128] R4 and R5 are each independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof.

[0129]

[0130] The group 4 element of M in the above chemical formulas 1 and 4 may be any one selected from the group consisting of Ti, Hf, and Zr.

[0131] In addition, X1 and X2 of the above chemical formulas 1 and 2 may be any one selected from the group consisting of Cl, Br, and I.

[0132] Meanwhile, R1 of the above chemical formula 2 may be phenyl, benzyl, o-toluidine substituted with one or more alkyl groups having 1 to 3 carbon atoms, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, or pentyl.

[0133] For example, R of Chemical Formula 2 1 In the case of o-toluidine, it may be a compound of chemical formula 2-1.

[0134]

[0135] [Chemical Formula 2-1]

[0136]

[0137]

[0138] X2 of the above chemical formula 2-1 may be any one selected from the group consisting of Cl, Br, and I.

[0139] The product of the reaction between the compound of Formula 1 and the compound of Formula 2 in the first step above can be represented as M(R1)4 (M is a Group 4 element, and R1 may be phenyl; benzyl; o-toluidine which is unsubstituted or substituted with one or more alkyl groups having 1 to 3 carbon atoms; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof).

[0140] The reaction solvents of the first step and the second step may be one or more selected from the group consisting of diethyl ether and tetrahydrofuran.

[0141] In addition, the reaction temperature of the first step and the second step may be room temperature (20~30℃). However, when adding the reactants for the reaction, the reaction temperature may be temporarily lowered to 0~10℃.

[0142] In one embodiment, a third step of reacting the compound of Formula 4 with a substituted or unsubstituted aromatic ring may be further included.

[0143] The reaction solvent of the third step above may be one or more selected from the group consisting of diethyl ether and tetrahydrofuran.

[0144] In addition, the reaction temperature of the third step may be room temperature (20~30℃).

[0145] When the above aromatic ring is substituted, the above aromatic ring may include one or more substituents, and each of the substituents may independently be hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; a linear or branched alkyl amine having 3 to 7 carbon atoms; or a combination thereof.

[0146] The above substituted or unsubstituted aromatic ring may be a substituted or unsubstituted aromatic ring with 5 or more carbon atoms.

[0147] In addition, the substituted or unsubstituted aromatic ring may be a heteroaromatic ring containing a substituted or unsubstituted oxygen atom or a nitrogen atom.

[0148] For example, the substituted or unsubstituted aromatic ring may be any one selected from the group consisting of substituted or unsubstituted pyrrole and substituted or unsubstituted cyclopentadiene.

[0149] In one embodiment, the substituted or unsubstituted pyrrole is represented by Chemical Formula 5, and

[0150] The above substituted or unsubstituted cyclopentadiene can be represented by Chemical Formula 6.

[0151]

[0152] [Chemical Formula 5]

[0153]

[0154]

[0155] In the above chemical formula 5,

[0156] R6 to R9 are each independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof.

[0157]

[0158] [Chemical Formula 6]

[0159]

[0160] In the above chemical formula 6,

[0161] R 10 to R 14 Each is independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; a linear or branched alkyl amine having 3 to 7 carbon atoms; or a combination thereof.

[0162] For example, the branched alkyl amine may be any one selected from the group consisting of dimethylamine, ethylmethylamine, and diethylamine.

[0163] For example, the substituted or unsubstituted cyclopentadiene may be one or more selected from the group consisting of cyclopentadiene, N-methyl 2-cyclopentadienyl propylamine, and 2-(cyclopentadienyl)-N,2-dimethylpropanamine.

[0164] In one embodiment, the compound of Formula 1, the compound of Formula 2, and the substituted or unsubstituted aromatic ring may be injected sequentially into a reactor, or the compound of Formula 1, the compound of Formula 2, and the substituted or unsubstituted aromatic ring may be injected simultaneously into a reactor.

[0165] In one embodiment, the metal compound may be one or more selected from the group consisting of the compound represented by Formula 7, the compound represented by Formula 8, and the compound represented by Formula 9.

[0166]

[0167] [Chemical Formula 7]

[0168]

[0169]

[0170] In the above chemical formula 7,

[0171] M is a group 4 element, and

[0172] R 15 to R 25 Each is independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof.

[0173]

[0174] [Chemical Formula 8]

[0175]

[0176]

[0177] In the above chemical formula 8,

[0178] M is a group 4 element, and

[0179] R 26 to R 33 Each is independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof.

[0180] In addition, Me in the above chemical formula 8 represents methyl.

[0181]

[0182] [Chemical Formula 9]

[0183]

[0184]

[0185] In the above chemical formula 9,

[0186] M is a group 4 element, and

[0187] R 34 to R 43 Each is independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof.

[0188] In one embodiment, the organometallic compound may be a vapor deposition precursor.

[0189] A method for manufacturing a thin film according to another aspect of the present invention may include: a first step of adsorbing a vapor deposition precursor comprising an organometallic compound manufactured by the manufacturing method onto a substrate and purging the unreacted vapor deposition precursor with an inert gas; and a second step of injecting a reaction gas to react with one or more of the adsorbed vapor deposition precursors and purging the unreacted reaction gas.

[0190] The above reaction gas can be activated by plasma.

[0191] In the deposition of the above organometallic compound, atomic layer deposition (ALD), which enables the deposition of nano-thick thin films with excellent uniformity even in complex three-dimensional structures, or organometallic chemical vapor deposition (MOCVD), in which all raw materials are supplied in a gaseous state and the amount of raw materials can be controlled relatively easily and accurately, may be used.

[0192] The above Step 1 and the subsequent Step 2 are combined to form one cycle, and the cycle can be repeated until a thin film of the desired thickness is obtained.

[0193] Additionally, the purging gas for the purging described above may include, but is not limited to, one or more selected from inert gases such as argon (Ar), nitrogen (N2), helium (He), or hydrogen (H2).

[0194] Depending on the thin film to be manufactured, the above reaction gas may include oxidizing agents, reducing agents, nitrating agents, etc., but is not limited thereto.

[0195] For example, the oxidizing agent may be water vapor (H2O), oxygen (O2), or ozone (O3), the reducing agent may be hydrogen (H2), ammonia (NH3), hydrazine (N2H4), borane (BH3), diborane (B2H6), etc., and the nitrating agent may be ammonia (NH3), hydrazine (N2H4), nitrogen (N2), etc.

[0196] The plasma that activates the above reaction gas may be a mixed plasma of Ar and H2, and by using the plasma, the reactivity of the reaction gas is improved to widen the process temperature range and lead to a complete reaction of the vapor deposition precursor, making it possible to form a thin film with low impurity content.

[0197] The present invention will be explained in more detail below using examples, but the present invention is not limited thereto.

[0198]

[0199] [Example 1] Synthesis of ZrCp(NMe2)3(ZrCp[N(CH3)2]3)

[0200]

[0201] Synthesis of tetrabenzyl zirconium (ZrBz4(Zr(CH2C6H5)4))

[0202] 200 ml of diethyl ether is added to a flask containing 0.43 mol of benzyl magnesium halide (halide can be Cl or Br) dissolved in 300 ml of diethyl ether.

[0203] Afterwards, zirconium chloride (Zirconium(IV) chloride, 0.11 mol) was slowly added at low temperature, raised to room temperature, and stirred overnight to synthesize tetrabenzyl zirconium (ZrBz4).

[0204] The NMR measurement results of the reaction products were as follows.

[0205]

[0206] 1 H-NMR (400MHz, Benzene-d6): δ 1.55(s, 8H), 6.38(t, 4H), 6.96(s, 8H), 7.06(t, 8H)

[0207]

[0208] Synthesis of tetradimethylamino zirconium (Zr(NMe2)4(Zr[N(CH3)2]4))

[0209] Dimethylamine (1.07 mol) was added to a flask containing synthesized tetrabenzyl zirconium (0.11 mol) at 0°C.

[0210] Afterwards, tetra-dimethylamino zirconium (Zr(NMe2)4) was synthesized by raising the temperature to room temperature and stirring.

[0211]

[0212] The NMR measurement results of the reaction products were as follows.

[0213]

[0214] 1 H-NMR (400 MHz, Benzene-d6): δ 2.99 (s, 24H)

[0215]

[0216] Synthesis of ZrCp(NMe2)3(ZrCp[N(CH3)2]3)

[0217] Cyclopentadiene (Cp, 0.11 mol) was added to a flask containing synthesized tetradimethylamino zirconium (0.11 mol), and the mixture was stirred at room temperature. When the reaction was complete, 500 ml of hexane was added to dilute the mixture, and it was filtered through a filter containing celite. The filtrate was then concentrated under reduced pressure to purify the synthesized ZrCp(NMe2)3.

[0218]

[0219] The yield of the reaction product and the NMR measurement results were as follows.

[0220]

[0221] Yield: 68%

[0222] 1 H-NMR (400 MHz, Benzene-d6): δ 2.96 (s, 6H), 6.03 (s, 5H)

[0223]

[0224] Each chemical reaction step and reaction product of the preparation process of ZrCp(NMe2)3(ZrCp[N(CH3)2]3) is shown in Fig. 1.

[0225]

[0226] [Example 2] Synthesis of CpC(CH3)2CH2NMeZr(NMe2)2

[0227]

[0228] Synthesis of Tetrabenzyl Zirconium and Tetradimethylamino Zirconium

[0229] Tetrabenzyl zirconium and tetradimethylamino zirconium were synthesized in the same manner as in Example 1.

[0230]

[0231] Synthesis of CpC(CH3)2CH2N(CH3)Zr(N(CH3)2)2

[0232] 2-(cyclopentadienyl)-N,2-dimethylpropanamine (0.21 mol) was added to a flask containing synthesized tetradimethylamino zirconium (0.21 mol), and then stirred at room temperature.

[0233] When the reaction was finished, 2 L of hexane was added to dilute it, and after filtering it through a filter containing celite, the filtrate was concentrated under reduced pressure to purify the synthesized CpC(CH3)2CH2NMeZr(NMe2)2.

[0234]

[0235] The yield of the reaction product and the NMR measurement results were as follows.

[0236]

[0237] Yield: 70%

[0238] 1 H-NMR (400MHz, Benzene-d6): δ 1.24(d, 3H), 2.94(d, 6H), 3.05(s, 3H), 3.65(m, 2H), 5.74(m,1H), 5.86(m,1H), 6.01(m, 1H), 6.05(m, 1H)

[0239]

[0240] [Example 3] Synthesis of HfCp(NMe2)3(ZrCp[N(CH3)2]3)

[0241]

[0242] Synthesis of tetrabenzyl hafnium (HfBz4(Hf(CH2C6H5)4))

[0243] 200 ml of diethyl ether is added to a flask containing 0.8 mol of benzyl magnesium halide (halide can be Cl or Br) dissolved in 500 ml of diethyl ether.

[0244] Afterwards, hafnium chloride (Hafnium(IV) chloride, 0.2 mol) was slowly added at low temperature, raised to room temperature, and stirred overnight to synthesize tetrabenzyl hafnium (Tetra-benzyl hafnium, HfBz4).

[0245] The NMR measurement results of the reaction products were as follows.

[0246]

[0247] 1 H-NMR (400 MHz, Benzene-d6): δ 1.49 (s, 8H), 6.53 (d, 8H), 6.94 (t, 4H), 7.08 (t, 8H)

[0248]

[0249] Synthesis of tetradimethylamino hafnium (Hf(NMe2)4(Hf[N(CH3)2]4))

[0250] Dimethylamine (2.0 mol) was added to a flask containing synthesized tetrabenzyl hafnium (0.2 mol) at 0°C.

[0251] Afterwards, tetra-dimethylamino hafnium (Hf(NMe2)4) was synthesized by raising the temperature to room temperature and stirring.

[0252]

[0253] The NMR measurement results of the reaction products were as follows.

[0254]

[0255] 1 H-NMR (400 MHz, Benzene-d6): δ 2.98 (s, 24H)

[0256]

[0257] Synthesis of HfCp(NMe2)3(HfCp[N(CH3)2]3)

[0258] Cyclopentadiene (Cp, 0.2 mol) was added to a flask containing synthesized tetradimethylamino hafnium (0.2 mol), and the mixture was stirred at room temperature. When the reaction was complete, 700 ml of hexane was added to dilute the mixture, and it was filtered through a filter containing celite. The filtrate was then concentrated under reduced pressure to purify the synthesized HfCp(NMe2)3.

[0259]

[0260] The yield of the reaction product and the NMR measurement results were as follows.

[0261]

[0262] Yield: 75%

[0263] 1 H-NMR (400 MHz, Benzene-d6): δ 2.95 (s, 6H), 6.03 (s, 5H)

[0264]

[0265] [Example 4] Synthesis of CpC(CH3)2CH2NMeHf(NMe2)2

[0266]

[0267] Synthesis of Tetrabenzyl Hafnium and Tetradimethylamino Hafnium

[0268] Tetrabenzyl hafnium and tetradimethylamino hafnium were synthesized in the same manner as in Example 3.

[0269]

[0270] Synthesis of CpC(CH3)2CH2N(CH3)Hf(N(CH3)2)2

[0271] 2-(cyclopentadienyl)-N,2-dimethylpropanamine (0.2 mol) was added to a flask containing synthesized tetradimethylamino hafnium (0.2 mol), and then stirred at room temperature.

[0272] When the reaction was finished, 2 L of hexane was added to dilute it, and after filtering through a filter containing celite, the filtrate was concentrated under reduced pressure to purify the synthesized CpC(CH3)2CH2NMeHf(NMe2)2.

[0273]

[0274] The yield of the reaction product and the NMR measurement results were as follows.

[0275]

[0276] Yield: 75%

[0277] 1 H-NMR (400MHz, Benzene-d6): δ 1.23(d, 3H), 3.0(d, 6H), 3.06(s, 3H), 3.69(m, 2H), 5.72(m,1H), 5.86(m,1H), 5.99(m, 1H), 6.03(m, 1H)

[0278]

[0279] [Preparation Example] Preparation of Zirconium and Hafnium Oxide Thin Films

[0280] A thin film was prepared by depositing ZrCp(NMe2)3, CpC(CH3)2CH2NMeZr(NMe2)2, HfCp(NMe2)3, or CpC(CH3)2CH2NMeHf(NMe2)2 prepared according to Examples 1 to 4 using an atomic layer deposition (ALD) device.

[0281] The substrate used was a bare Si wafer, and prior to deposition, it was cleaned by ultrasonic treatment in acetone, ethanol, and deionized water (DI water) for 10 minutes each. The native oxide film on the bare Si wafer was removed by immersing it in a 10% HF solution (HF:H2O=1:9) for 10 seconds. The bare Si wafer cleaned with HF was immediately transferred to an atomic layer deposition (ALD) chamber. The temperature was maintained at 105°C.

[0282] [Zirconium or hafnium precursors of Examples 1 to 4] (X seconds) - [Ar] (10 seconds) - [O3] (Y seconds) - [Ar] (10 seconds), and 100 cycles were performed with the above sequence as one cycle. At this time, the zirconium precursor of Example 1 or Example 2 was dissolved in one or more organic solvents selected from hexane, octane, and cyclopentyl methyl ether (15% by weight or less) and supplied to the deposition chamber through a liquid delivery system.

[0283] In the present example of preparation, the selectivity of hexane, octane, and cyclopentyl methyl ether is not specifically limited, but the use of octane or cyclopentyl methyl ether is preferred.

[0284] In the supply of the source gas, the zirconium or hafnium precursor of Examples 1 to 4 (X seconds), X was set to 3 seconds to 15 seconds (3, 5, 7, 10, 13, and 15 seconds, respectively), and the supply of the reaction gas, ozone (O3) (Y seconds), was set to 1 second to 5 seconds (1, 3, and 5 seconds, respectively). The flow rate of argon (Ar) for purging was set to 100 sccm, and the reaction gas, ozone (O3), was flowed. Each reaction gas was injected by controlling the on / off of the pneumatic valve. It was confirmed that a zirconium or hafnium oxide thin film was formed by setting the reactor pressure to 1 torr within a process temperature (substrate temperature) range of 260°C to 340°C.

[0285]

[0286] As described above, through the method for manufacturing organometallic compounds of the present invention, it was possible to safely synthesize organometallic compounds with high reaction yields at a low manufacturing cost.

[0287] In addition, it was confirmed that a metal thin film was formed as a result of preparing a metal thin film using the above organometallic compound as a vapor deposition precursor.

[0288]

[0289] The scope of the present invention is defined by the claims set forth below rather than by the detailed description above, and all modifications or variations derived from the meaning and scope of the claims and equivalent concepts thereof should be interpreted as being included within the scope of the present invention.

[0290] The method for manufacturing an organometallic compound according to the present invention has the effect of improving the reaction yield of the organometallic compound, lowering manufacturing costs, and improving stability.

[0291] In addition, a thin film produced by a method for producing a thin film using an organometallic compound produced by the method for producing an organometallic compound of the present invention as a vapor deposition precursor has excellent physical properties, and said thin film can be used in various electronic devices, particularly semiconductors, displays, solar cells, etc.

Claims

1. A first step of reacting a compound of Chemical Formula 1 with a compound of Chemical Formula 2; and A second step of synthesizing a compound of Formula 4 by reacting the product of the reaction in the first step with a compound of Formula 3; comprising Method for preparing organometallic compounds. [Chemical Formula 1] M(X1)4 In the above chemical formula 1, M is a group 4 element, and X1 is a halogen atom. [Chemical Formula 2] R1-Mg-X2 In the above chemical formula 2, R1 is phenyl; benzyl; o-toluidine that is unsubstituted or substituted with one or more alkyl groups having 1 to 3 carbon atoms; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof, X2 is a halogen atom. [Chemical Formula 3] HNR2R3 In the above chemical formula 3, R2 and R3 are each independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof. [Chemical Formula 4] M(NR4R5)4 In the above chemical formula 4, M is a group 4 element, and R4 and R5 are each independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof.

2. In Paragraph 1, A third step further comprising reacting the compound of Chemical Formula 4 with a substituted or unsubstituted aromatic ring, Method for preparing organometallic compounds.

3. In Paragraph 2, The above substituted or unsubstituted aromatic ring is any one selected from the group consisting of substituted or unsubstituted pyrrole and substituted or unsubstituted cyclopentadiene, Method for preparing organometallic compounds.

4. In Paragraph 3, The above-mentioned substituted or unsubstituted pyrrole is represented by Chemical Formula 5, and The above-mentioned substituted or unsubstituted cyclopentadiene is represented by Chemical Formula 6, Method for preparing organometallic compounds. [Chemical Formula 5] In the above chemical formula 5, R6 to R9 are each independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof. [Chemical Formula 6] In the above chemical formula 6, R 10 to R 14 Each is independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; a linear or branched alkyl amine having 3 to 7 carbon atoms; or a combination thereof.

5. In Paragraph 3, The substituted or unsubstituted cyclopentadiene is one or more selected from the group consisting of cyclopentadiene, N-methyl 2-cyclopentadienyl propylamine, and 2-(cyclopentadienyl)-N,2-dimethylpropanamine. Method for preparing organometallic compounds.

6. In Paragraph 2, The compound of Formula 1, the compound of Formula 2, and the substituted or unsubstituted aromatic ring are sequentially injected into a reactor, or A compound of Formula 1, a compound of Formula 2, and a substituted or unsubstituted aromatic ring are simultaneously injected into a reactor. Method for preparing organometallic compounds.

7. In Paragraph 1, The above organometallic compound is one or more selected from the group consisting of the compound represented by Formula 7, the compound represented by Formula 8, and the compound represented by Formula 9, Method for preparing organometallic compounds. [Chemical Formula 7] In the above chemical formula 7, M is a group 4 element, and R 15 to R 25 Each is independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof. [Chemical Formula 8] In the above chemical formula 8, M is a group 4 element, and R 26 to R 33 Each is independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof, and Me is a methyl group. [Chemical Formula 9] In the above chemical formula 9, M is a group 4 element, and R 34 to R 43 Each is independently hydrogen; a linear or branched hydrocarbon having 1 to 5 carbon atoms; or a combination thereof.

8. In Paragraph 1, The above organometallic compound is a vapor deposition precursor, Method for preparing organometallic compounds.

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