Intermediate and method for preparing thin-film-forming precursor compound using intermediate

Abstract

The present invention relates to a method for preparing an intermediate for the preparation of a thin-film-forming precursor compound, the method comprising a step for mixing an alkali metal compound and an organic solvent to form a mixed solution, and adding a central metal supply material and an amine compound to the mixed solution to form a reaction solution, wherein the process of forming the mixed solution and the reaction solution is carried out as a single-step process in a single reactor.

Description

Method for producing an intermediate and a precursor compound for forming a thin film using the intermediate

[0001] The present invention relates to an intermediate of a precursor compound for forming a thin film and a method for producing a precursor compound for forming a thin film using the intermediate, and more particularly, to an improved intermediate of a precursor compound capable of simplifying the entire manufacturing process of a precursor compound and reducing carbon emissions by optimizing a process for synthesizing an intermediate in a process for synthesizing a metal-containing compound used as a precursor in a thin film forming process, and a method for producing a precursor compound for forming a thin film using the intermediate.

[0002] Semiconductor thin films are generally thin films containing metal, and are formed through a process of depositing precursors. Organometallic compounds are often used as precursors. Organometallic compounds used as precursors in common deposition processes such as chemical vapor deposition (CVD) and atomic layer deposition (ALD) include not only simple organometallic compounds with a single ligand bonded to a central metal atom, but also complex organometallic compounds with different ligands bonded, taking deposition efficiency into account.

[0003] In order to manufacture such organometallic compounds for precursors, an intermediate is manufactured, and the desired organometallic compound is obtained through a secondary reaction of the intermediate. Since the intermediate must be manufactured through multiple step reactions, the reaction conditions must be continuously controlled, and in order to perform low-temperature reactions or long-term reactions, a lot of carbon emissions are inevitably generated in obtaining the final product.

[0004] For example, Korean Patent Publication No. 10-2022-0087046 describes a process for producing a Group 4 transition metal-containing compound represented by Chemical Formula 1, comprising the steps of: obtaining a mixed solution by stirring an organic solvent (hexane) and an alkali metal compound (n-butyllithium) at a low temperature of -30°C; adding an amine compound (dimethylamine) to the mixed solution and raising the temperature to -10°C to form an alkali metal-amine compound (Li-DMA); cooling the reaction solution to -30°C again, adding a Group 4 metal supplying material (hafnium chloride), and raising the temperature to room temperature to produce an intermediate; and adding a ligand supplying material (methylcyclopentadiene) to the intermediate to obtain the desired precursor compound (bis(dimethylamino)(i-propoxy)(methylcyclopentadienyl)hafnium).

[0005] Examining the manufacturing processes of these conventional technologies reveals that producing intermediates requires controlled temperature conditions and reaction times, and requires multi-step reactions. Therefore, applying these manufacturing processes presents the problem of requiring complex, lengthy processes to obtain the desired precursor compound.

[0006] The present invention has been conceived in consideration of the above-described prior art, and its purpose is to provide an economical and environmentally friendly manufacturing process by simplifying the manufacturing process of an intermediate in the manufacturing process of a precursor compound used as a precursor for forming a thin film, thereby increasing process efficiency and production yield and reducing carbon emissions that may occur during the process.

[0007] In particular, the purpose is to provide a manufacturing method that is optimized for the manufacturing of an organometallic compound containing an amine ligand and can simplify the manufacturing process of an intermediate.

[0008] The method for producing an intermediate of a precursor compound for forming a thin film of the present invention for achieving the above-described purpose is a method for producing an intermediate used in a process for producing a precursor compound for forming a thin film, comprising the steps of mixing an alkali metal compound and an organic solvent to form a mixed solution, and adding a central metal supply material and an amine compound to the mixed solution to form a reaction solution, and is characterized in that the process of forming the mixed solution and the reaction solution is performed in a single reactor as a one-step process.

[0009] At this time, in the step of forming the reaction solution, the central metal supply material and the amine compound can be introduced at a temperature of -40 to 0°C.

[0010] Additionally, the formed reaction solution can react at a temperature of 80°C or lower to form an intermediate.

[0011] Additionally, the amine compound may be one or more of a primary amine, a secondary amine, and a tertiary amine.

[0012] In addition, the method for manufacturing the intermediate may have a total process time of 10 hours or less.

[0013] Additionally, the central metal supply material may be a metal halide and may include any one element selected from a group 4, group 5 or group 6 transition metal as the central metal.

[0014] In addition, the precursor for forming a thin film of the present invention is characterized in that it is manufactured by using an intermediate obtained according to the above manufacturing method and reacting the intermediate and a ligand supply material.

[0015] By using the intermediate obtained through the manufacturing method of the present invention, the manufacturing process of the intermediate can be simplified in the manufacturing process of the precursor compound used as a precursor for forming a thin film, thereby increasing the efficiency and production yield of the manufacturing process and reducing carbon emissions that may occur during the process, thereby manufacturing the desired precursor compound economically and environmentally friendly.

[0016] In particular, the purpose of the manufacturing method of the present invention is to provide a manufacturing method that is optimized for the manufacturing of an organometallic compound containing an amine ligand and can simplify the manufacturing process of an intermediate.

[0017] Figure 1 is a diagram of a product according to Example 1-1. 1 This is the result of H-NMR analysis.

[0018] Figure 2 is a product according to Example 1-2. 1 This is the result of H-NMR analysis.

[0019] Figure 3 is a product according to Example 2-1. 1 This is the result of H-NMR analysis.

[0020] Figure 4 is a product according to Example 2-2. 1 This is the result of H-NMR analysis.

[0021] Figure 5 is a product according to Example 3-1. 1 This is the result of H-NMR analysis.

[0022] Figure 6 is a product according to Example 3-2. 1 This is the result of H-NMR analysis.

[0023] Figure 7 is a product according to Example 4-1. 1 This is the result of H-NMR analysis.

[0024] Figure 8 is a product according to Example 4-2. 1 This is the result of H-NMR analysis.

[0025] Figure 9 is a product according to Example 5-1. 1 This is the result of H-NMR analysis.

[0026] Figure 10 is a product according to Example 5-2.1 This is the result of H-NMR analysis.

[0027] Figure 11 is a product according to Example 6-1. 1 This is the result of H-NMR analysis.

[0028] Figure 12 is a product according to Example 6-2. 1 This is the result of H-NMR analysis.

[0029] Figure 13 is a product according to Example 7-1. 1 This is the result of H-NMR analysis.

[0030] Figure 14 is a product according to Example 7-2. 1 This is the result of H-NMR analysis.

[0031] Figure 15 is a product according to Example 8-1. 1 This is the result of H-NMR analysis.

[0032] Figure 16 is a product according to Example 8-2. 1 This is the result of H-NMR analysis.

[0033] Figure 17 is a product according to Example 9-1. 1 This is the result of H-NMR analysis.

[0034] Fig. 18 is a product according to Example 9-2. 1 This is the result of H-NMR analysis.

[0035] Figure 19 is a product according to Example 11-1. 1 This is the result of H-NMR analysis.

[0036] Figure 20 is a product according to Example 12-1. 1 This is the result of H-NMR analysis.

[0037] Fig. 21 is a product according to Example 13-1. 1 This is the result of H-NMR analysis.

[0038] Fig. 22 is a product according to Example 14-1. 1 This is the result of H-NMR analysis.

[0039] 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.

[0040] The present invention relates to a method for preparing an intermediate used in a process for preparing a precursor compound for forming a thin film, particularly a precursor compound containing an amine ligand, and has a technical feature that allows an intermediate, which was conventionally prepared through a multi-step reaction, to be prepared through a single-step reaction. To this end, the method for preparing an intermediate of the present invention includes a step of forming a mixed solution by mixing an alkali metal compound and an organic solvent, and adding a central metal supply material and an amine compound to the mixed solution to form a reaction solution, wherein the process of forming the mixed solution and the reaction solution can be performed as a single-step process in a single reactor.

[0041] Precursor compounds containing amine ligands are usually manufactured via an aminated metal intermediate. An example of a process for manufacturing tris(dimethylamido)cyclopentadienyl metal compounds (CpM), such as tris(dimethylamido)cyclopentadienyl titanium (CpTi), tris(dimethylamido)cyclopentadienyl hafnium (CpHf), and tris(dimethylamido)cyclopentadienyl zirconium (CpZr), which are widely used in the process of forming Group 4 metal-containing thin films, is manufactured through a three-step reaction as shown in Scheme 1 below.

[0042] [Reaction Formula 1]

[0043]

[0044] In step 1, an alkali metal compound and an amine compound react in a solvent to produce an alkali metal-amine compound, and in step 2, an intermediate, tetra(dimethylamino) metal (TDMAM), is produced by a reaction between the alkali metal-amine compound and a metal chloride (Group 4 metal). Finally, in step 3, the intermediate, TDMAM, reacts with cyclopentadiene (CpH), a ligand supplying material, to produce the desired CpM.

[0045] This reaction pathway suffers from low production efficiency due to the significant processing time required for steps 1 and 2 to form the intermediate. Process testing revealed that step 1 required 14 hours of reaction and processing time, while step 2 required 6 hours. Once the intermediate is formed, the third step to obtain the final product only takes 2 hours. Therefore, the intermediate formation step acts as a bottleneck, reducing the efficiency of the overall process.

[0046] As an example of the conventional reaction route for producing CpHf, first, an n-BuLi solution and hexane as a solvent are introduced into a reactor and cooled to -15°C. Next, dimethylamine (DMA) is slowly introduced into the n-BuLi solution, and after the introduction of DMA is complete, the temperature is slowly raised to room temperature and the reaction is performed. In addition, after the reaction is complete, the remaining DMA is removed. After the DMA is completely removed, the reactor is cooled to 0-10°C and HfCl4 is slowly introduced. After the introduction is complete, the temperature is raised to 60°C and the reaction is performed to obtain the intermediate TDMAHf. Finally, the reactor containing TDMAHf is cooled to -10°C and CpH is slowly introduced to synthesize the target CpHf.

[0047] In the above reaction path, the state in which DMA residue is completely removed and only pure Li-Dimethylamine exists is the first-stage reaction, and the above process causes the first-stage reaction to take a long time. In addition, the second-stage reaction in which an intermediate is produced requires time to lower the temperature that has been raised after the first-stage reaction and to raise the temperature after adding HfCl4 to complete the reaction. Therefore, the process time for temperature control is added, and the reaction takes the longest time.

[0048] On the other hand, in the manufacturing method of the present invention, the process of forming the mixed solution and the reaction solution is carried out in a single step, so the reaction time is significantly reduced. The entire reaction path for manufacturing the CpM according to the manufacturing method of the present invention is comprised of two steps, as shown in Scheme 2 below.

[0049] [Reaction Formula 2]

[0050]

[0051] According to Scheme 2, the formation of the intermediate TDMAM proceeds in a single step, simplifying the reaction and shortening the reaction time to 8 hours, significantly reducing the overall synthesis time for the precursor compound. Furthermore, since the intermediate formation process is completed within a single reactor, production facilities can be simplified.

[0052] In the above reaction path, it is preferable that the central metal supply material and the amine compound are introduced at a temperature of -40 to 0°C.

[0053] In addition, in the process of forming an intermediate from the above reaction solution, the intermediate can be formed by reacting for 3 to 5 hours at a reaction temperature of 80°C or lower, preferably 60 to 80°C, and more preferably 40 to 80°C, so the intermediate can be obtained with a shorter reaction time compared to the conventional intermediate production process.

[0054] In addition, although dimethylamine is used as an example of an amine compound in the above reaction formula 2, various amine compounds selected from primary amines, secondary amines, or tertiary amines including the dimethylamine may also be applied.

[0055] In addition, it was found that a metal halide is suitable as the central metal supply material, and a Group 4, Group 5, or Group 6 transition metal can also be applied as the central metal. Therefore, the manufacturing method of the present invention can be applied to a process for synthesizing a precursor compound for forming a Group 4, Group 5, or Group 6 transition metal-containing thin film.

[0056] For example, the process for manufacturing CpHf involves placing n-BuLi solution and hexane in a reactor, cooling to -15°C, adding HfCl4 to the n-BuLi solution, slowly adding DMA, slowly raising the temperature to room temperature, and carrying out a reaction at 60°C to obtain the intermediate TDMAHf. In addition, after the intermediate formation reaction is complete, the reactor temperature is lowered to -10°C again, and CpH is slowly added to obtain the desired CpHf.

[0057] In order to simplify the conventional synthetic method, if n-BuLi, HfCl4, and DMA are introduced at once in the presence of a solvent, HfCl4 may react with n-BuLi to cause a side reaction, or impurities may be generated, affecting the yield and purity of the intermediate. For this reason, the reaction must proceed in step 2 by forming Li-DMA in step 1 and then introducing HfCl4. In this reaction, in order to suppress the side reaction of HfCl4 reacting with n-BuLi during the reaction in step 1, HfCl4 is introduced at an internal temperature of -15℃ in the reactor, and then DMA is slowly introduced and reacted at the same temperature of -15℃. In this reaction, the reaction can proceed without a side reaction even if HfCl4, n-BuLi, and DMA react in step 1.

[0058] Using the intermediate produced by this reaction, the desired precursor compound can be easily manufactured. This can be manufactured by adding a ligand supplying material to the intermediate and reacting it. The step of synthesizing this final precursor compound can be performed under the same conditions as conventional synthetic methods. However, the manufacturing method of the present invention simplifies the intermediate synthesis process, which is the bottleneck of the reaction, thereby improving the efficiency of the overall manufacturing process.

[0059] Hereinafter, the effects of the present invention will be explained through examples.

[0060] [Example 1-1] Synthesis of TDMAHf

[0061] In a vacuum-dried 500㎖ Schrank flask, 54.2g (197mmol) of n-BuLi solution (2.5M in hexane) and 195㎖ of hexane were diluted, and the internal temperature was maintained at -15℃. 15g (46.83 mmol) of HfCl4 (Hafnium chloride) diluted with 30㎖ of hexane was added dropwise and stirred. Subsequently, 11.08g (245mmol) of DMA (Dimethylamine) was slowly added dropwise, and the reaction was carried out while stirring at 60℃ for 4 hours. After the reaction, the filter was carried out using a glass filter with Celite, and the obtained pale yellow liquid was distilled under reduced pressure of 0.1 Torr at 50℃ to obtain 15g (90%) of pale yellow solid. The melting point of the pale yellow solid was 26-29℃.

[0062] 1 The results of H-NMR analysis are as shown in Fig. 1, and it was confirmed that TDMAHf was synthesized from the characteristic peak detected at 2.99 (s, 24H).

[0063] [Example 1-2] Synthesis of CpHf(DMA)3

[0064] Into a vacuum-dried 500㎖ Schrank flask, 15g (42.2mmol) of TDMAHf prepared in Example 1-1 was placed, 195㎖ of hexane was added, and the mixture was cooled to -15℃. 2.79g (42.2mmol) of CpH (Cyclopentadiene) was slowly added dropwise, and the mixture was allowed to warm to room temperature and reacted at 40℃ for 1 hour. The yellow liquid obtained after the reaction was distilled under reduced pressure of 0.1 Torr at 50℃ to obtain 15.5g (97.5%) of a yellow liquid, and the boiling point of this yellow liquid was 75℃ / 0.2 Torr.

[0065] 1The results of H-NMR analysis are as shown in Fig. 2, and it was confirmed that CpHf(DMA)3 was synthesized from the characteristic peaks detected at 6.0(s, 5H) and 3.0(s, 18H).

[0066] [Example 2-1] Synthesis of TDMAZr

[0067] In a vacuum-dried 500㎖ Schrank flask, 74.98g (270mmol) of n-BuLi solution (2.5M in hexane) and 195㎖ of hexane were diluted, and the internal temperature was maintained at -15℃. 15g (64.36 mmol) of ZrCl4 (zirconium chloride) diluted with 30㎖ of hexane was added dropwise and stirred. Next, 15.08g (334 mmol) of DMA (dimethylamine) was slowly added dropwise, and the reaction was carried out while stirring at 60℃ for 4 hours. After the reaction, the filter was carried out using a glass filter with Celite, and the obtained pale yellow liquid was distilled under reduced pressure of 0.1 Torr at 50℃ to obtain 16.71g (90%) of pale yellow solid. The melting point of the pale yellow solid was 57-60℃.

[0068] 1 The results of H-NMR analysis are as shown in Fig. 3, and it was confirmed that TDMAZr was synthesized from the characteristic peak detected at 2.97 (s, 24H).

[0069] [Example 2-2] Synthesis of CpZr(DMA)3

[0070] Into a vacuum-dried 500 ml Schrank flask, 15 g (56 mmol) of TDMAZr prepared in Example 2-1 was placed, 195 ml of hexane was added, and the mixture was cooled to -15°C. 3.7 g (56 mmol) of CpH (Cyclopentadiene) was slowly added dropwise, the mixture was warmed to room temperature, and then reacted at 40°C for 1 hour. The yellow liquid obtained after the reaction was distilled under reduced pressure of 0.1 Torr at 50°C to obtain 15.5 g (97.5%) of a yellow liquid, and the boiling point of this yellow liquid was 86°C / 0.1 Torr.

[0071] 1 The results of H-NMR analysis are as shown in Fig. 4, and it was confirmed that CpZr(DMA)3 was synthesized from the characteristic peaks detected at 6.05 (s, 5H) and 2.92 (s, 18H).

[0072] [Example 3-1] Synthesis of TDMATi

[0073] In a vacuum-dried 500㎖ Schrank flask, 92.13g (332mmol) of n-BuLi solution (2.5M in hexane) and 195㎖ of hexane were diluted, and the internal temperature was maintained at -15℃. 15g (79.08mmol) of TiCl4 (titanium chloride) diluted with 30㎖ of hexane was added dropwise and stirred. Subsequently, 18.53g (411mmol) of DMA (dimethylamine) was slowly added dropwise, and the reaction was carried out with stirring at 60℃ for 4 hours. After the reaction, the filter was carried out using a glass filter with Celite, and the obtained red liquid was distilled under reduced pressure of 0.1 Torr at 50℃ to obtain 16.48g (85%) of red liquid. The boiling point of the liquid was 50℃ / 0.055 Torr.

[0074] 1 The results of H-NMR analysis are as shown in Fig. 5, and it was confirmed that TDMATi was synthesized from the characteristic peak of 3.11 (s, 24H) detected.

[0075] [Example 3-2] Synthesis of CpTi(DMA)3

[0076] In a vacuum-dried 500 ml Schrank flask, 15 g (67 mmol) of TDMATi prepared in Example 3-1 was placed, 195 ml of hexane was added, and the mixture was cooled to -15°C. 4.42 g (67 mmol) of CpH (Cyclopentadiene) was slowly added dropwise, the mixture was warmed to room temperature, and then reacted at 40°C for 1 hour. The red liquid obtained after the reaction was distilled under reduced pressure of 0.1 Torr at 50°C to obtain 15.7 g (95.7%) of a red solid. The boiling point of the red solid was 75°C / 0.2 Torr.

[0077] 1 The results of H-NMR analysis are as shown in Fig. 6, and it was confirmed that CpTi(DMA)3 was synthesized from the characteristic peaks detected at 5.94 (s, 5H) and 3.08 (s, 18H).

[0078] [Example 4-1] Synthesis of TEMAHf

[0079] In a vacuum-dried 500㎖ Schrank flask, 54.2g (197mmol) of n-BuLi solution (2.5M in hexane) and 195㎖ of hexane were diluted, and the internal temperature was maintained at -15℃. 15g (46.83mmol) of HfCl4 (Hafnium chloride) diluted with 30㎖ of hexane was added dropwise and stirred. Next, 14.4g (243.6mmol) of EMA (Ethylmethylamine) was slowly added dropwise, and the reaction was carried out with stirring at 60℃ for 4 hours. After the reaction, the solution was filtered using a glass filter containing Celite, and the obtained pale yellow liquid was distilled under reduced pressure at 50℃ and 0.1 Torr to obtain 18g (93%) of a yellow liquid. The boiling point of the yellow liquid was 79℃ / 0.1 Torr.

[0080] 1 The results of H-NMR analysis are as shown in Figure 7, and it was confirmed that TEMAHf was synthesized from the characteristic peaks detected at 3.28 (q, 8H), 2.99 (s, 12H), and 1.16 (t, 12H).

[0081] [Example 4-2] Synthesis of CpHf(EMA)3

[0082] 15 g (36.5 mmol) of TEMAHf prepared in Example 4-1 was placed in a vacuum-dried 500 mL Schrank flask, 195 mL of hexane was added, and the mixture was cooled to -15°C. 2.41 g (36.5 mmol) of CpH (Cyclopentadiene) was slowly added dropwise, the mixture was warmed to room temperature, and then reacted at 40°C for 1 hour. The yellow liquid obtained after the reaction was distilled under reduced pressure of 0.1 Torr at 50°C to obtain 14.5 g (95%) of a yellow liquid. The boiling point of the yellow liquid was 90°C / 0.1 Torr.

[0083] 1 The results of H-NMR analysis are as shown in Fig. 8, and it was confirmed that CpHf(EMA)3 was synthesized from the characteristic peaks detected at 6.06 (s, 5H), 3.24 (q, 8H), 2.91 (s, 12H), and 1.05 (t, 8H).

[0084] [Example 5-1] Synthesis of TEMAZr

[0085] In a vacuum-dried 500㎖ Schrank flask, 54.2g (197mmol) of n-BuLi solution (2.5M in hexane) and 195㎖ of hexane were diluted, and the internal temperature was maintained at -15℃. 15g (64.36mmol) of ZrCl4 (zirconium chloride) diluted with 30㎖ of hexane was added dropwise and stirred. Next, 19.8g (334.4mmol) of EMA (Ethylmethylamine) was slowly added dropwise, and the reaction was carried out with stirring at 60℃ for 4 hours. After the reaction, the filter was carried out using a glass filter with Celite glassware, and the obtained pale yellow liquid was distilled under reduced pressure at 50℃ and 0.1 Torr to obtain 18.2g (87.3%) of a yellow liquid. The boiling point of the yellow liquid was 83℃ / 0.1 Torr.

[0086] 1The results of H-NMR analysis are as shown in Fig. 9, and it was confirmed that TEMAZr was synthesized from the characteristic peaks detected at 3.24 (q, 8H), 2.99 (s, 12H), and 1.16 (t, 12H).

[0087] [Example 5-2] Synthesis of CpZr(EMA)3

[0088] In a vacuum-dried 500 ml Schrank flask, 15 g (46.3 mmol) of TEMAZr prepared in Example 5-1 was placed, 195 ml of hexane was added, and the mixture was cooled to -15°C. 3.06 g (46.3 mmol) of CpH (Cyclopentadiene) was slowly added dropwise, the mixture was warmed to room temperature, and then reacted at 40°C for 1 hour. The yellow liquid obtained after the reaction was distilled under reduced pressure of 0.1 Torr at 50°C to obtain 14.4 g (94%) of a yellow liquid. The boiling point of the yellow liquid was 92°C / 0.2 Torr.

[0089] 1 The results of H-NMR analysis are as shown in Fig. 10, and it was confirmed that CpZr(EMA)3 was synthesized from the characteristic peaks detected at 6.09 (s, 5H), 3.22 (q, 8H), 2.88 (s, 12H), and 1.05 (t, 8H).

[0090] [Example 6-1] Synthesis of TEMATi

[0091] In a vacuum-dried 500㎖ Schrank flask, 54.2g (197mmol) of n-BuLi solution (2.5M in hexane) and 195㎖ of hexane were diluted, and the internal temperature was maintained at -15℃. 15g (79.08mmol) of TiCl4 (titanium chloride) diluted with 30㎖ of hexane was added dropwise and stirred. Next, 24.3g (410.8mmol) of EMA (ethylmethylamine) was slowly added dropwise, and the reaction was carried out with stirring at 60℃ for 4 hours. After the reaction, the filter was carried out using a glass filter with Celite, and the obtained red liquid was distilled under reduced pressure of 0.1 Torr at 50℃ to obtain 19.8g (89%) of red liquid. The boiling point of the red liquid was 95℃ / 0.2 Torr.

[0092] 1 The results of H-NMR analysis are as shown in Figure 11, and it was confirmed that TEMAZTi was synthesized from the characteristic peaks detected at 3.46 (q, 8H), 3.12 (s, 12H), and 1.12 (t, 12H).

[0093] [Example 6-2] Synthesis of CpTi(EMA)3

[0094] In a vacuum-dried 500 ml Schrank flask, 15 g (53.5 mmol) of TEMATi prepared in Example 6-1 was placed, 195 ml of hexane was added, and the mixture was cooled to -15°C. 3.53 g (53.5 mol) of CpH (Cyclopentadiene) was slowly added dropwise, the mixture was warmed to room temperature, and then reacted at 40°C for 1 hour. The red liquid obtained after the reaction was distilled under reduced pressure of 0.1 Torr at 50°C to obtain 14.5 g (93.6%) of a red liquid. The boiling point of the red liquid was 105°C / 0.2 Torr.

[0095] 1The results of H-NMR analysis are as shown in Figure 12, and it was confirmed that CpTi(EMA)3 was synthesized from the characteristic peaks detected at 5.97 (s, 5H), 3.45 (q, 8H), 3.06 (s, 12H), and 1.02 (t, 8H).

[0096] [Example 7-1] Synthesis of TDEAHf

[0097] In a vacuum-dried 500㎖ Schrank flask, 54.2g (197mmol) of n-BuLi solution (2.5M in hexane) and 195㎖ of hexane were diluted, and the internal temperature was maintained at -15℃. 15g (46.83mmol) of HfCl4 (Hafnium chloride) diluted with 30㎖ of hexane was added dropwise and stirred. Subsequently, 17.8g (243.5mmol) of DEA (Diethylamine) was slowly added dropwise, and the reaction was carried out with stirring at 60℃ for 4 hours. After the reaction, the solution was filtered using a glass filter containing Celite, and the obtained pale yellow liquid was distilled under reduced pressure at 50℃ and 0.1 Torr to obtain 19.7g (90%) of a yellow liquid. The boiling point of the yellow liquid was 90℃ / 0.2 Torr.

[0098] 1 The results of H-NMR analysis are as shown in Figure 13, and it was confirmed that TDEAHf was synthesized from the characteristic peaks detected at 3.37 (q, 16H) and 1.16 (t, 24H).

[0099] [Example 7-2] Synthesis of CpHf(DEA)3

[0100] Into a vacuum-dried 500 ml Schrank flask, 15 g (42.3 mmol) of TDEAHf prepared in Example 7-1 was placed, 195 ml of hexane was added, and the mixture was cooled to -15°C. 2.79 g (42.3 mmol) of CpH (Cyclopentadiene) was slowly added dropwise, the mixture was warmed to room temperature, and then reacted at 40°C for 1 hour. The yellow liquid obtained after the reaction was distilled under reduced pressure of 0.1 Torr at 50°C to obtain 14.1 g (95.4%) of a yellow liquid. The boiling point of the yellow liquid was 102°C / 0.2 Torr.

[0101] 1 The results of H-NMR analysis are as shown in Figure 14, and it was confirmed that CpHf(DEA)3 was synthesized from the characteristic peaks detected at 6.09 (s, 5H), 3.29 (q, 12H), and 1.03 (t, 18H).

[0102] [Example 8-1] Synthesis of TDEAZr

[0103] In a vacuum-dried 500㎖ Schrank flask, 54.2g (197mmol) of n-BuLi solution (2.5M in hexane) and 195㎖ of hexane were diluted, and the internal temperature was maintained at -15℃. 15g (64.36mmol) of ZrCl4 (zirconium chloride) diluted with 30㎖ of hexane was added dropwise and stirred. Subsequently, 24.4g (334.4mmol) of DEA (diethylamine) was slowly added dropwise, and the reaction was carried out with stirring at 60℃ for 4 hours. After the reaction, the solution was filtered using a glass filter containing Celite, and the obtained pale yellow liquid was distilled under reduced pressure at 50℃ and 0.1 Torr to obtain 22.5g (92%) of a yellow liquid. The boiling point of the yellow liquid was 85℃ / 0.1 Torr.

[0104] 1 The results of H-NMR analysis are as shown in Figure 15, and it was confirmed that TDEAZr was synthesized from the characteristic peaks detected at 3.35 (q, 16H) and 1.16 (t, 24H).

[0105] [Example 8-2] Synthesis of CpZr(DEA)3

[0106] Into a vacuum-dried 500 ml Schrank flask, 15 g (56.1 mmol) of TDEAZr prepared in Example 8-1 was placed, 195 ml of hexane was added, and the mixture was cooled to -15°C. 3.7 g (56.1 mmol) of CpH (Cyclopentadiene) was slowly added dropwise, the mixture was warmed to room temperature, and then reacted at 40°C for 1 hour. The yellow liquid obtained after the reaction was distilled under reduced pressure of 0.1 Torr at 50°C to obtain 13.5 g (91.7%) of a yellow liquid. The boiling point of the yellow liquid was 106°C / 0.1 Torr.

[0107] 1 The results of H-NMR analysis are as shown in Figure 16, and it was confirmed that CpZr(DEA)3 was synthesized from the characteristic peaks detected at 6.12 (s, 5H), 3.28 (q, 12H), and 1.03 (t, 18H).

[0108] [Example 9-1] Synthesis of TDEATi

[0109] In a vacuum-dried 500㎖ Schrank flask, 54.2g (197mmol) of n-BuLi solution (2.5M in hexane) and 195㎖ of hexane were diluted, and the internal temperature was maintained at -15℃. 15g (79.08mmol) of TiCl4 (titanium chloride) diluted with 30㎖ of hexane was added dropwise and stirred. Subsequently, 32.5g (410.8mmol) of DEA (diethylamine) was slowly added dropwise, and the reaction was carried out with stirring at 60℃ for 4 hours. After the reaction, the solution was filtered using a glass filter containing Celite, and the obtained red liquid was distilled under reduced pressure at 50℃ and 0.1 Torr to obtain 24.1g (90.6%) of a red liquid. The boiling point of the red liquid was 99℃ / 0.1 Torr.

[0110] 1The results of H-NMR analysis are as shown in Figure 17, and it was confirmed that TDEATi was synthesized from the characteristic peaks detected at 3.59 (q, 16H) and 1.11 (t, 24H).

[0111] [Example 9-2] Synthesis of CpTi(DEA)3

[0112] Into a vacuum-dried 500 ml Schrank flask, 15 g (66.9 mmol) of TDEATi prepared in Example 9-1 was placed, 195 ml of hexane was added, and the mixture was cooled to -15°C. 4.42 g (66.9 mmol) of CpH (Cyclopentadiene) was slowly added dropwise, the mixture was warmed to room temperature, and then reacted at 40°C for 1 hour. The red liquid obtained after the reaction was distilled under reduced pressure of 0.1 Torr at 50°C to obtain 13.2 g (89.9%) of a red liquid. The boiling point of the red liquid was 110°C / 0.1 Torr.

[0113] 1 The results of H-NMR analysis are as shown in Figure 18, and it was confirmed that CpTi(DEA)3 was synthesized from the characteristic peaks detected at 6.00 (s, 5H), 3.55 (q, 12H), and 1.00 (t, 18H).

[0114] [Example 10-1] Synthesis of TDMAVo

[0115] In a vacuum-dried 500㎖ Schrank flask, 51.4g (184.7mmol) of n-BuLi solution (2.5M in hexane) and 51.4㎖ of hexane were diluted, and the internal temperature was maintained at -15℃. 10g (57.7mmol) of VOCl3 (Vanadium oxytrichloride) diluted with 20㎖ of hexane was added dropwise and stirred. Next, 10.41g (230.8mmol) of DMA (Dimethylamine) was slowly added dropwise, and the reaction was carried out with stirring at 60℃ for 4 hours. After the reaction, the glass filter was filtered using a Celite-containing glass filter, and the obtained dark green liquid was distilled under reduced pressure of 0.1 Torr at 50℃ to obtain 9.19g (80%) of a white solid.

[0116] [Example 11-1] Synthesis of PDMANb

[0117] In a vacuum-dried 500㎖ Schrank flask, 53.6g (193mmol) of n-BuLi solution (2.5M in hexane) and 51.4㎖ of hexane were diluted, and the internal temperature was maintained at -15℃. 10g (37mmol) of NbCl5 (Niobium chloride) diluted with 20㎖ of hexane was added dropwise and stirred. Next, 10.85g (240.6mmol) of DMA (Dimethylamine) was slowly added dropwise, and the reaction was carried out with stirring at 60℃ for 4 hours. After the reaction, the glass filter was filtered using a Celite-insulated glass filter, and the obtained brown liquid was distilled under reduced pressure of 0.1 Torr at 50℃ to obtain 10.12g (85%) of a dark purple solid.

[0118] 1 The results of H-NMR analysis are as shown in Figure 19, and it was confirmed that PDMANb was synthesized from the characteristic peak detected at 3.18 (s, 30H).

[0119] [Example 12-1] Synthesis of PDMATa

[0120] In a vacuum-dried 500㎖ Schrank flask, 53.6g (145.2mmol) of n-BuLi solution (2.5M in hexane) and 51.4㎖ of hexane were diluted, and the internal temperature was maintained at -15℃. 10g (27.9mmol) of TaCl5 (Tantalum chloride) diluted with 20㎖ of hexane was added dropwise and stirred. Next, 8.18g (181.5mmol) of DMA (Dimethylamine) was slowly added dropwise, and the reaction was carried out with stirring at 60℃ for 4 hours. After the reaction, the glass filter was filtered using a Celite-insulated glass filter, and the obtained brown liquid was distilled under reduced pressure of 0.1 Torr at 50℃ to obtain 13.51g (92%) of a colored solid.

[0121] 1 The results of H-NMR analysis are as shown in Fig. 20, and it was confirmed that PDMATa was synthesized from the characteristic peak detected at 3.26 (s, 30H).

[0122] [Example 13-1] Synthesis of PDMAMo

[0123] In a vacuum-dried 500㎖ Schrank flask, 63.21g (227mmol) of n-BuLi solution (2.5M in hexane) and 51.4㎖ of hexane were diluted, and the internal temperature was maintained at -15℃. 10g (37mmol) of MoCl5 (molybdenum chloride) diluted with 20㎖ of hexane was added dropwise and stirred. Next, 12.38g (275mmol) of DMA (dimethylamine) was slowly added dropwise, and the reaction was carried out with stirring at 60℃ for 4 hours. After the reaction, the glass filter was filtered using a Celite-insulated glass filter, and the obtained brown liquid was distilled under reduced pressure of 0.1 Torr at 50℃ to obtain 9.97g (81%) of a brown solid.

[0124] 1The results of H-NMR analysis are as shown in Fig. 21, and it was confirmed that PDMAMo was synthesized from the characteristic peak detected at 3.28 (s, 30H).

[0125] [Example 14-1] Synthesis of HDMAW

[0126] In a vacuum-dried 500㎖ Schrank flask, 53.6g (156mmol) of n-BuLi solution (2.5M in hexane) and 51.4㎖ of hexane were diluted, and the internal temperature was maintained at -15℃. 10g (25.2mmol) of WCl6 (Tungsten hexachloride) diluted with 20㎖ of hexane was added dropwise and stirred. Next, 8.52g (189.1mmol) of DMA (Dimethylamine) was slowly added dropwise, and the reaction was carried out with stirring at 60℃ for 4 hours. After the reaction, the mixture was filtered using a glass filter containing Celite, and the obtained orange liquid was distilled under reduced pressure of 0.1 Torr at 50℃ to obtain 9.85g (86%) of a red solid.

[0127] 1 The results of H-NMR analysis are as shown in Figure 22, and it was confirmed that HDMAW was synthesized from the characteristic peak detected at 3.45 (s, 36H).

[0128] 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 method for producing an intermediate for producing a precursor compound for forming a thin film, It comprises a step of forming a mixed solution by mixing an alkali metal compound and an organic solvent, and adding a central metal supply material and an amine compound to the mixed solution to form a reaction solution. A method for producing an intermediate of a precursor compound for forming a thin film, characterized in that the process of forming the above mixed solution and reaction solution is performed as a one-step process in a single reactor.

2. In claim 1, A method for producing an intermediate of a precursor compound for forming a thin film, characterized in that, in the step of forming the above reaction solution, a central metal supply material and an amine compound are introduced at a temperature of -40 to 0°C.

3. In claim 1, A method for producing an intermediate of a precursor compound for forming a thin film, characterized in that the formed reaction solution reacts at a temperature of 80°C or lower to form an intermediate.

4. In claim 1, A method for producing an intermediate of a precursor compound for forming a thin film, characterized in that the above amine compound is one or more of a primary amine, a secondary amine, and a tertiary amine.

5. In claim 1, A method for producing an intermediate of a precursor compound for forming a thin film, characterized in that the entire process time is 10 hours or less.

6. In claim 1, A method for producing an intermediate of a precursor compound for forming a thin film, characterized in that the central metal supply material is a metal halide.

7. In claim 1, A method for producing an intermediate of a precursor compound for forming a thin film, characterized in that the central metal supply material comprises any one element selected from group 4, group 5, and group 6 transition metals as a central metal.

8. A method for producing a precursor compound for forming a thin film using an intermediate obtained according to the manufacturing method of claim 1, A method for producing a precursor compound for forming a thin film, characterized in that the precursor compound for forming a thin film is produced by reacting the intermediate and ligand supply material.

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