Novel compound, precursor composition containing the same, and method for producing a thin film using the same.

Abstract

The present invention relates to a gas-phase deposition compound that enables thin film deposition via gas-phase deposition, and more specifically, to a novel compound applicable to atomic layer deposition (ALD) or chemical vapor deposition (CVD) and exhibiting excellent reactivity, volatility, and thermal stability, a precursor composition containing the novel compound, and a method for producing a thin film using the precursor composition.

Description

[Technical Field]

[0001] The present invention relates to a novel compound capable of thin film deposition via vapor phase deposition, a precursor composition containing the novel compound, and a method for producing a thin film using the precursor composition. [Background technology]

[0002] As semiconductor devices become more highly integrated and miniaturized, it is becoming increasingly important to form thin metal and metal oxide films of uniform thickness for application in various technologies such as microelectrons, magnetic information storage, and catalysts.

[0003] Chemical vapor deposition (CVD) or atomic layer deposition (ALD) are used to manufacture metal and metal oxide thin films. In particular, atomic layer deposition allows for the formation of desired thin films by sequentially injecting and removing reactants into a chamber, making composition adjustment easy and enabling the formation of thin films with uniform thickness. Furthermore, atomic layer deposition has the advantage of excellent step coverage, allowing for the uniform growth of thin films on complex and intricate devices.

[0004] Precursors play a crucial role in the production of thin films using atomic layer deposition (ADD), requiring high volatility, high thermal stability, and high reactivity within the chamber. To date, precursor development has progressed by applying various ligands, with well-known representative ligands including halogens, alkoxides, cyclopentadienes, β-diketones, amides, and amidinates. However, most known precursors are solid compounds, or have low volatility or stability, or can cause problems such as impurity contamination during thin film deposition. Therefore, there is a need for the development of novel precursors with superior properties that overcome these shortcomings.

[0005] In particular, silicon dioxide (SiO2) has been used as the gate dielectric material for transistors until now. However, as the size of semiconductor devices has been gradually decreasing, problems such as tunneling current leakage, resulting increase in power dissipation and heat generation have become serious. Therefore, the need to develop new materials with higher dielectric constants to replace SiO2 dielectrics has emerged.

[0006] Group IV metals such as hafnium or zirconium are widely used as high dielectric constant thin film materials due to their relatively wide bandgap energy, high Si integration, and high interchangeability. However, existing precursor materials used in the production of hafnium or zirconium thin films have limitations in improving the deposition rate, uniformity, flatness, and purity of the thin films, and the development of improved precursors is needed. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Korean Published Patent No. 2011-0065383 [Patent Document 2] Korean Published Patent No. 2014-0029428 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] The present invention aims to provide novel group 4 metal element-containing compounds and precursor compositions containing the same, applicable to atomic layer deposition (ALD) or chemical vapor deposition (CVD).

[0009] In particular, the objective is to provide a precursor composition that is liquid, can be purified at low temperatures, has excellent thermal stability and volatility, and allows for thin-film deposition over a wide temperature range.

[0010] Furthermore, the present invention aims to provide a method for producing a thin film using the precursor composition described above.

[0011] However, the problems to be solved by the present application are not limited to the problems mentioned above, and other problems not mentioned may be clearly understood by those skilled in the art from the following description.

Means for Solving the Problems

[0012] One aspect of the present application provides a compound represented by the following Chemical Formula 1:

Chemical Formula

[0013] In the above Chemical Formula ①, M is titanium (Ti), zirconium (Zr), or hafnium (Hf); R1 to R4 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms; R5 to R 10 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 4 carbon atoms.

[0014] Another aspect of the present application provides a precursor composition for vapor deposition containing the above compound.

[0015] Still another aspect of the present application provides a method for manufacturing a thin film including the step of introducing the above precursor composition for vapor deposition into a chamber.

Advantages of the Invention

[0016] [[ID=四十二]] The novel compound according to the present invention and the precursor composition containing the novel compound are excellent in reactivity, volatility, and thermal stability, are liquids, and enable uniform thin film deposition with excellent properties, thereby ensuring excellent thin film physical properties, thickness, and step coverage property.

[0017] The physical properties as described above provide a precursor suitable for atomic layer deposition and chemical vapor deposition.

Brief Description of the Drawings

[0018] It should be noted that in the translation, "①" in "In the above Chemical Formula ①" should be replaced with the correct formula number or symbol in the original text. Also, "四十二" in "[[ID=四十二]] " seems to be an incorrect ID number in the original, which should be corrected as well. [Figure 1] This graph shows the change in deposition rate of the Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl)hafnium compound in Example 2 of this application, with respect to the change in process temperature. [Figure 2] This graph shows the change in deposition rate of the Tris(dimethylamido)(2,5-di-ethyl-1H-pyrrolyl)hafnium compound in Example 3 of this application, with respect to the change in process temperature. [Modes for carrying out the invention]

[0019] The operation and effects of the invention will be described in more detail below through specific embodiments of the invention. However, these embodiments are presented merely as examples of the invention and do not determine the scope of the invention's rights.

[0020] Prior to this, terms and words used in this specification and claims should not be interpreted in a manner limited to their ordinary or dictionary meanings, but rather in a manner consistent with the technical idea of ​​the present invention, based on the principle that inventors may define the concepts of terms as appropriate to describe their invention in the best possible way.

[0021] Therefore, the configurations of the embodiments described herein represent only one of the most preferred embodiments of the present invention and do not represent the entire technical concept of the present invention. It should be understood that various equivalents and modifications may exist that can substitute for these at the time of filing.

[0022] In this specification, singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, terms such as “includes,” “equip,” or “have” are intended to specify the existence of implemented features, figures, steps, components, or combinations thereof, and should be understood not to preemptively exclude the existence or possibility of adding one or more other features, figures, steps, components, or combinations thereof.

[0023] In this specification, in numerical ranges "a to b" and "a~b", "to" and "~" are defined as ≥ a and ≤ b.

[0024] A compound according to one aspect of this invention can be represented by the following chemical formula 1. [ka]

[0025] In the aforementioned chemical formula 1, M is titanium (Ti), zirconium (Zr), or hafnium (Hf); R1 to R4 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms; R5~R 10 These are, independently, hydrogen and a linear or branched hydrocarbon group having 1 to 4 carbon atoms.

[0026] In one embodiment of the present application, preferably, R1 to R4 may each be independently selected from the group consisting of hydrogen, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, sec-pentyl group, tert-pentyl group, hexyl group, isohexyl group, and isomers thereof.

[0027] R1 to R4 may more preferably be any one selected from the group consisting of hydrogen, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, and tert-butyl group, but are not limited thereto.

[0028] More preferably, R1 and R4 are ethyl groups, iso-propyl groups, or tert-butyl groups, and R2 and R3 may be hydrogen. In the case of compounds having hydrocarbon groups other than the aforementioned hydrocarbon groups, the compound may be in a solid state rather than a liquid state, or its thermal stability may be inferior to that of the compounds of this application.

[0029] In one implementation example of the present invention, preferably R5~R 10 Each of these may be independently selected from the group consisting of hydrogen, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, and tert-butyl group.

[0030] R5~R 10 More preferably, each of these may be independently selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group, but is not limited thereto.

[0031] More preferably, R5~R 10 Each of these groups may independently be an ethyl group or a methyl group. In the case of compounds having hydrocarbon groups other than the aforementioned hydrocarbon groups, the compound may be in a solid state rather than a liquid state, or its thermal stability may be inferior to that of the compounds of this application.

[0032] In one embodiment of the present invention, the chemical formula 1 can be represented by the following chemical formulas 1-1, 1-2, or 1-3.

[0033] [ka] [ka] [ka]

[0034] In the chemical formulas 1-1, 1-2, and 1-3 above, M is titanium (Ti), zirconium (Zr), or hafnium (Hf).

[0035] In other words, examples of M(Pyrrole)(Amide) compounds represented by the above chemical formula 1 include, but are not limited to, the following hafnium and zirconium compounds: Tris(dimethylamido)(2,5-di-tert-butyl-1H-pyrrolyl)hafnium Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl)hafnium Tris(dimethylamido)(2,5-di-ethyl-1H-pyrrolyl)hafnium; Tris(dimethylamido)(2,5-di-tert-butyl-1H-pyrrolyl)zirconium Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl)zirconium.

[0036] In one embodiment of the present invention, the compound represented by chemical formula 1 may be a liquid at room temperature. Furthermore, the compound represented by chemical formula 1 has a low melting point and excellent volatility at low temperatures.

[0037] A precursor composition for vapor deposition according to one aspect of the present invention may contain any one of the compounds represented by chemical formula 1.

[0038] A method for manufacturing a thin film according to one aspect of the present invention may include the step of introducing the vapor deposition precursor composition into a chamber.

[0039] In one embodiment of the present invention, the step of introducing the vapor deposition precursor composition into a chamber may include steps of physical adsorption, chemisorption, or both physical and chemisorption.

[0040] In one embodiment of the present invention, the method for manufacturing the thin film may include both atomic layer deposition (ALD) and chemical vapor deposition (CVD).

[0041] More specifically, the deposition method may include metal-organic chemical vapor deposition (MOCVD), low-pressure chemical vapor deposition (LPCVD), pulsed chemical vapor deposition (P-CVD), plasma-enhanced atomic layer deposition (PE-ALD), or a combination thereof.

[0042] The method for manufacturing the thin film may preferably be atomic layer deposition, but is not limited thereto.

[0043] In atomic layer deposition (ALD), reactants must be highly volatile, stable, and highly reactive. ALD is a method in which reactants are supplied separately, and during one deposition cycle, a thin film of monolayer or less grows through surface reactions. Ligands of reactants adsorbed on the substrate are removed through chemical reactions with other reactants supplied thereafter. When heating the precursor compounds, which are reactants for atomic layer deposition, being in the liquid phase can be significantly more advantageous in terms of reaction rate and process than being in the solid phase.

[0044] In one embodiment of the present invention, the method for producing the thin film may further include the step of injecting one or more reaction gases selected from hydrogen (H2), oxygen (O) atom-containing compounds (or mixtures), nitrogen (N) atom-containing compounds (or mixtures), or silicon (Si) atom-containing compounds (or mixtures) as a reaction gas.

[0045] Specifically, one or more of the following can be used as reaction gases: hydrogen (H2), water vapor (H2O), oxygen (O2), ozone (O3), nitrogen (N2), ammonia (NH3), hydrazine (N2H4), or silane.

[0046] More specifically, water vapor (H2O), oxygen (O2), and ozone (O3) can be used as reaction gases for depositing oxide thin films, and nitrogen (N2), ammonia (NH3), or hydrazine (N2H4) can be used as reaction gases for depositing nitride thin films. Furthermore, hydrogen (H2) can be used as a reaction gas for depositing metal thin films, and silane compounds can also be used.

[0047] Preferably, water vapor (H2O), oxygen (O2), ozone (O3), or a combination thereof can be used as the reaction gas for depositing the oxide thin film.

[0048] In one embodiment of the present invention, if the method for manufacturing the thin film is atomic layer deposition (ALD), the invention may include a first purging step of purging the precursor composition from the chamber before the step of injecting the reaction gas and / or a second purging step of purging by-products that do not react with the precursor composition or are generated by such reaction after the step of injecting the reaction gas.

[0049] The purging step assists in the movement of the precursor onto the substrate, ensures that the inside of the reactant group has a pressure suitable for deposition, and releases impurities present inside the reactant group to the outside. In other words, a further step may be performed to purge the reactant group with an inert gas such as argon (Ar), nitrogen (N2), or helium (He) before and after the supply of the reaction gas.

[0050] In one embodiment of the present invention, the method for manufacturing the thin film may have a process temperature of 100°C or more and 500°C or less.

[0051] For example, the process temperature may be 150°C to 480°C, 200°C to 460°C, or 230°C to 440°C. Preferably, the process temperature may be 250°C to 410°C.

[0052] In one embodiment of the present invention, the method for manufacturing the thin film may involve a canister temperature of -20°C or higher and 110°C or lower.

[0053] For example, the canister temperature may be 0°C to 105°C, 20°C to 100°C, 40°C to 95°C, 60°C to 90°C, 70°C to 80°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C. The canister temperature may preferably be 80°C.

[0054] A canister is used to supply a source gas into a reaction chamber in a thin film manufacturing method. Typically, the canister vaporizes a precursor composition to generate a source gas, and then supplies that source gas into the chamber.

[0055] When the canister temperature is below -20°C or above 110°C, the uniformity of the thickness of the thin film produced by the thin film manufacturing method may decrease significantly. This is because, below -20°C, the amount of precursor composition supplied to the chamber is insufficient, and above 110°C, it is difficult to obtain a uniform film quality due to alteration caused by thermal energy or an excessive supply of precursor composition to the chamber.

[0056] In one embodiment of the present invention, the injection time of the precursor composition may be 1 second or more and 30 seconds or less, and the injection amount of the precursor composition transport gas may be 10 sccm or more and 1000 sccm or less.

[0057] For example, the injection time of the precursor composition may be 1 second to 29 seconds, 4 seconds to 27 seconds, 7 seconds to 25 seconds, 10 seconds to 23 seconds, 13 seconds to 21 seconds, or 15 seconds to 20 seconds. The amount of purge gas injected in the first purge step may be 20 sccm to 800 sccm, 40 sccm to 700 sccm, 60 sccm to 600 sccm, 80 sccm to 500 sccm, 100 sccm to 450 sccm, 150 sccm to 400 sccm, or 250 sccm to 350 sccm.

[0058] If the process proceeds with the above-mentioned ranges being exceeded or not met, it may be difficult to form a suitable thin film.

[0059] Specifically, if the injection time of the precursor composition is less than 1 second, there may be insufficient reactants necessary for thin film formation, and a thin film of appropriate thickness may not be formed. On the other hand, if the injection time of the precursor composition exceeds 30 seconds, the composition ratio of the produced thin film may become inconsistent due to impurities from residual compounds after the reaction.

[0060] Furthermore, if the injection amount of the precursor composition transport gas is less than 10 sccm, the residual amount of the precursor composition, which is the reactant, will increase, which may lead to an improper reaction, resulting in impurities not being purged and the thin film layer being deposited unevenly.

[0061] In one embodiment of the present invention, the injection time of the reaction gas may be 1 second or more and 30 seconds or less, and the injection volume of the reaction gas may be 50 sccm or more and 3000 sccm or less.

[0062] For example, the injection time of the reaction gas may be 2 seconds to 25 seconds, 2 seconds to 20 seconds, 3 seconds to 15 seconds, or 3 seconds to 10 seconds. Preferably, the injection time of the reaction gas may be 3 seconds to 7 seconds.

[0063] Furthermore, the amount of reaction gas injected may be, for example, 100 sccm or more and 2500 sccm or less, 300 sccm or more and 2000 sccm or less, 500 sccm or more and 1500 sccm or less, 700 sccm or more and 1300 sccm or less, or 900 sccm or more and 1100 sccm or less.

[0064] Furthermore, if the injection volume of the reaction gas is less than 50 sccm, the residual amount of the precursor composition, which is the reactant, increases, which may lead to an improper reaction, the generation of impurities, and the uneven deposition of the thin film layer. On the other hand, if the injection volume of the reaction gas exceeds 3000 sccm, impurities due to the reaction gas compounds may be generated.

[0065] In one embodiment of the present invention, the purge gas injection time of the first purge step is 1 second or more and 1 minute or less, the purge gas injection time of the second purge step is 10 seconds or more and 1 minute or less, and the amount of purge gas injected in the first purge step and the second purge step may be independently 100 sccm or more and 2000 sccm or less.

[0066] For example, the purge gas injection time in the first purge step may be 3 seconds or more and 55 seconds or less, 6 seconds or more and 50 seconds or less, 9 seconds or more and 45 seconds or less, 12 seconds or more and 40 seconds or less, or 15 seconds or more and 35 seconds, and the purge gas injection time in the second purge step may be 10 seconds or more and 60 seconds or less, 20 seconds or more and 55 seconds or less, or 30 seconds or more and 50 seconds. The amount of purge gas injected in the first purge step and the second purge step is independently set to 100 sccm to 200 sccm, 100 sccm to 300 sccm, 100 sccm to 400 sccm, 100 sccm to 500 sccm, 100 sccm to 600 sccm, 100 sccm to 700 sccm, 100 sccm to 800 sccm, 100 sccm to 900 sccm, 100 sccm to 1000 sccm, and 100 sccm to 1200 sccc. It may also be less than or equal to m, between 100 sccm and 1400 sccm, between 100 sccm and 1600 sccm, between 100 sccm and 1800 sccm, between 200 sccm and 1700 sccm, between 300 sccm and 1600 sccm, between 400 sccm and 1600 sccm, between 500 sccm and 1600 sccm, between 600 sccm and 1600 sccm, between 700 sccm and 1600 sccm, between 800 sccm and 1600 sccm, or between 900 sccm and 1600 sccm.

[0067] In one embodiment of the present invention, the number of repetitions of the cycle may be 10 or more.

[0068] For example, the number of repetitions of the cycle may be 10 or more, 100 or more, 200 or more, 500 or more, 1,000 or more, 5,000 or more, 10,000 or more, 50,000 or more, or 100,000 or more but not exceeding 1,000,000.

[0069] If the above-mentioned process conditions for the reaction gas, process temperature, precursor composition, and purge gas are not met, a thin film with excellent properties cannot be obtained. [Examples]

[0070] The present invention will be described in more detail below through the examples. However, the following examples are for the purpose of further illustrating the present invention, and the scope of the present invention is not limited by the following examples. [Example of combination] Synthesis Example 1: Synthesis of 2,2,7,7-tetramethyloctane-3,6-dione Potassium hydride (in THF) was placed in a flask, and 3,3-dimethylbutan-2-one was slowly added at 0°C, stirring for 1 hour. After that, copper(II) chloride (Cu Cl2)(in DMF) was slowly added at -78°C, stirred at 60°C for 3 hours, and then stirred at room temperature for 24 hours. The flask temperature was lowered, 1M HCl was added and the reaction was carried out (work up), and then diethyl ether, water (H2O), and brine were added to extract the compound. The extracted compound was dried over MgSO4, and the filtrate was collected through a filter and concentrated under reduced pressure to obtain 2,2,7,7-tetramethyloctane-3,6-dione.

[0071] The chemical structure and NMR measurement results for the obtained 2,2,7,7-tetramethyloctane-3,6-dione are as follows. [Chemical structural formula of 2,2,7,7-tetramethyloctane-3,6-dione] [ka] 1 H-NMR (400 MHz, CDCl3): δ 1.17 (s, 9H), 2.76 (s, 2H)

[0072] Synthesis Example 2: Synthesis of 2,5-di-tert-butyl-1H-pyrrole ligand 2,2,7,7-tetramethyloctane-3,6-dione obtained in Synthesis Example 1, acetic acid, and ammonium acetate were placed in a flask and stirred at 100°C for 4 hours. After stirring, an aqueous solution of potassium carbonate was slowly added to the compound, and the compound was extracted using diethyl ether, deionized water (DIW), and brine. The extracted compound was dried over MgSO4, and the filtrate was collected through a filter. After concentration under reduced pressure, purification was carried out. The synthesized 2,5-di-tert-butyl-1H-pyrrole was a clear liquid compound with a synthesis yield of 55%.

[0073] The chemical structure and NMR measurement results of the synthesized 2,5-di-tert-butyl-1H-pyrrole are as follows. [Chemical structural formula of 2,5-di-tert-butyl-1H-pyrrole] [ka] 1 H-NMR (400 MHz, CDCl3): δ 1.30 (s, 9H), 5.8 (d, 2H)

[0074] Synthesis Example 3: Synthesis of 2,7-dimethyloctane-3,6-dione Potassium hydride (in THF) was placed in a flask, and 3-methylbutan-2-one was slowly added at 0°C while stirring for 1 hour. Then, copper(II) chloride (CuCl2) (in DMF was slowly added at -78°C and stirred at room temperature for 24 hours. The flask temperature was lowered, 1M HCl was added and the reaction was carried out (work up), and then the compound was extracted with diethyl ether, water (H2O), and brine. The extracted compound was dried using MgSO4, and the filtrate was collected through a filter and concentrated under reduced pressure to obtain 2,7-dimethyloctane-3,6-dione.

[0075] The chemical structure and NMR measurement results for the obtained 2,7-dimethyloctane-3,6-dione are as follows. [Chemical structural formula of 2,7-dimethyloctane-3,6-dione] [ka] 1 H-NMR (400 MHz, CDCl3): δ1.1(d, 12H), 2.6(m, 2H), 2.7(s, 4H)

[0076] Synthesis Example 4: Synthesis of 2,5-di-isopropyl-1H-pyrrole ligand 2,7-dimethyloctane-3,6-dione obtained in Synthesis Example 3, acetic acid, and ammonium acetate were placed in a flask and stirred at 100°C for 4 hours. After stirring, an aqueous solution of potassium carbonate was slowly added to the compound, and the compound was extracted using diethyl ether, deionized water (DIW), and brine. The extracted compound was dried over MgSO4, and the filtrate was collected through a filter. After concentration under reduced pressure, purification was carried out. The synthesized 2,5-di-isopropyl-1H-pyrrole was a clear liquid compound with a synthesis yield of 30%.

[0077] The chemical structural formula and NMR measurement results of the synthesized 2,5-di-isopropyl-1H-pyrrole are as follows. [Chemical structural formula of 2,5-di-isopropyl-1H-pyrrole] [Chem.] 1 H-NMR (400 MHz, CDCl3): δ 1.4 (d, 12H), 2.9 (m, 2H), 5.8 (s, 2H)

[0078] Synthesis Example 5: Synthesis of Octane-3,6-Zeon Nitroalkane and potassium carbonate were placed in a flask, dissolved in water, and then stirred at room temperature for 5 minutes. Then, enone was added and stirred at room temperature for 3 hours, and 30% hydrogen peroxide was added and stirred at room temperature. After reacting with diethyl ether, water (H2O), and brine (work up), it was dried using MgSO4. Then, the filtered filtrate was obtained through a filter and concentrated under reduced pressure to obtain octane-3,6-dione.

[0079] The chemical structural formula and NMR measurement results of the obtained octane-3,6-dione are as follows. [Chemical structural formula of octane-3,6-dione] [Chem.] 1 H-NMR (400 MHz, CDCl3): δ 1.10 (t, 6H), 2.50 (q, 4H), 2.70 (s, 4H)

[0080] Synthesis Example 6: Synthesis of 2,5-di-ethyl-1H-pyrrole ligand Octane-3,6-dione obtained in Synthesis Example 5, acetic acid, and ammonium acetate were placed in a flask and stirred at 100°C for 4 hours. After stirring, an aqueous solution of potassium carbonate was slowly added to the compound, and the compound was extracted using diethyl ether, deionized water (DIW), and brine. The extracted compound was dried over MgSO4, and the filtrate was collected through a filter. After concentration under reduced pressure, purification was carried out. The synthesized 2,5-di-ethyl-1H-pyrrole was a clear liquid compound with a synthesis yield of 70%.

[0081] The chemical structure and NMR measurement results of the synthesized 2,5-di-ethyl-1H-pyrrole are as follows. [Chemical structural formula of 2,5-di-ethyl-1H-pyrrole] [ka] 1 H-NMR (400 MHz, CDCl3): δ1.3(t, 6H), 2.6(q, 4H), 2.7(s, 2H)

[0082] Example 1: Preparation of Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl)hafnium Tetrakis(dimethylamido)hafnium (TDMAH) was placed in a flask and diluted with toluene. The temperature was then lowered to 0°C, and 2,5-di-tert-butyl-1H-pyrrole (Synthesis Example 2), diluted in toluene, was slowly added while stirring. After all the compounds had been added, the mixture was stirred at room temperature for 24 hours. Subsequently, the solvent was concentrated under reduced pressure to secure the compound, and Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl)hafnium was obtained by purification under reduced pressure of the secured compound. The synthesized Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl)hafnium was a red liquid compound, and the synthesis yield was 40%.

[0083] The chemical structure and NMR measurement results of the synthesized Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl)hafnium are as follows. [Chemical structural formula of Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl)hafnium] [ka] 1 H-NMR (400 MHz, C6D6): δ1.40(s, 18H), 2.98(s, 18H), 6.20(s, 2H)

[0084] Example 2: Preparation of Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl)hafnium Tetrakis(dimethylamido)hafnium (TDMAH) was placed in a flask and diluted with toluene. The temperature was then lowered to 0°C, and 2,5-di-isopropyl-1H-pyrrole (Synthesis Example 4), diluted in toluene, was slowly added while stirring. After all the compounds had been added, the mixture was stirred at room temperature for 24 hours. Subsequently, the solvent was concentrated under reduced pressure to secure the compound, and Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl)hafnium was obtained by purification under reduced pressure of the secured compound. The synthesized Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl)hafnium was a yellow liquid compound, and the synthesis yield was 50%.

[0085] The chemical structure and NMR measurement results of the synthesized Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl)hafnium are as follows. [Chemical structural formula of Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl)hafnium] [ka] 1 H-NMR (400 MHz, C6D6): δ1.35(d, 12H), 2.98(s, 18H), 3.09(m, 2H), 6.18(s, 2H)

[0086] Example 3: Preparation of Tris(dimethylamido)(2,5-di-ethyl-1H-pyrrolyl)hafnium Tetrakis(dimethylamido)hafnium (TDMAH) was placed in a flask and diluted with toluene. The temperature was then lowered to 0°C, and 2,5-di-ethyl-1H-pyrrole (Synthesis Example 6), diluted in toluene, was slowly added while stirring. After all the compounds had been added, the mixture was stirred at room temperature for 24 hours. Subsequently, the solvent was concentrated under reduced pressure to secure the compound, and Tris(dimethylamido)(2,5-di-ethyl-1H-pyrrolyl)hafnium was obtained by purification under reduced pressure of the secured compound. The synthesized Tris(dimethylamido)(2,5-di-ethyl-1H-pyrrolyl)hafnium was a yellow liquid compound, and the synthesis yield was 50%.

[0087] The chemical structure and NMR measurement results of the synthesized Tris(dimethylamido)(2,5-di-ethyl-1H-pyrrolyl)hafnium are as follows. [Chemical structural formula of Tris(dimethylamido)(2,5-di-ethyl-1H-pyrrolyl)hafnium] [ka] 1 H-NMR (400 MHz, C6D6): δ1.3(t, 6H), 2.7(q, 4H), 2.9(s, 18H), 6.1(s, 2H)

[0088] Example 4: Preparation of Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl)zirconium Tetrakis(dimethylamido)zirconium (TDMAZ) was placed in a flask and diluted with toluene. The temperature was then lowered to 0°C, and 2,5-di-tert-butyl-1H-pyrrole (Synthesis Example 2), diluted in toluene, was slowly added while stirring. After all the compounds had been added, the mixture was stirred at room temperature for 24 hours. Subsequently, the solvent was concentrated under reduced pressure to secure the compound, and Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl)zirconium was obtained by purification under reduced pressure of the secured compound. The synthesized Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl)zirconium was a red liquid compound, and the synthesis yield was 38%.

[0089] The chemical structure and NMR measurement results of the synthesized Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl)zirconium are as follows. [Chemical structural formula of Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl)zirconium] [ka] 1 H-NMR (400 MHz, C6D6): δ1.40(s, 18H), 2.96(s, 18H), 6.19(s, 2H)

[0090] Example 5: Preparation of Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl)zirconium Tetrakis(dimethylamido)zirconium (TDMAZ) was placed in a flask and diluted with toluene. The temperature was then lowered to 0°C, and 2,5-di-isopropyl-1H-pyrrole (Synthesis Example 4), diluted in toluene, was slowly added while stirring. After all the compounds had been added, the mixture was stirred at room temperature for 24 hours. Subsequently, the solvent was concentrated under reduced pressure to secure the compound, and Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl)zirconium was obtained by purification of the secured compound under reduced pressure. The synthesized Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl)zirconium was a yellow liquid compound, and the synthesis yield was 51%.

[0091] The chemical structure and NMR measurement results of the synthesized Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl)zirconium are as follows. [Chemical structural formula of Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl)zirconium] [ka] 1 H-NMR (400 MHz, C6D6): δ1.34(d, 12H), 2.97(s, 18H), 3.05(m, 2H), 6.16(s, 2H)

[0092] [Manufacturing example] Manufacturing Example 1: Manufacturing of Hafnium Thin Films Using Atomic Layer Deposition (ALD) 1 A hafnium thin film was produced by atomic layer deposition (ALD) using the hafnium compound (Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl)hafnium) synthesized in Example 2 as a precursor.

[0093] The substrate used in this experiment was a p-type Si wafer with a resistance of 0.02 Ω·cm. Prior to deposition, the p-type Si wafer was sonicated in acetone, ethanol, and deionized water (DI water) for 10 minutes each. The native oxide thin film on the Si wafer was removed by immersing it in a 10% HF (HF:H2O=1:9) solution for 10 seconds. The HF-cleaned Si wafer was immediately transferred to an atomic layer deposition (ALD) chamber.

[0094] Water vapor (H2O) was used as the reaction gas, and it was injected at a flow rate of 1,000 sccm by adjusting the on / off switch of the pneumatic valve. For purging the precursor compound and reaction gas, argon (Ar), an inert gas, was used at a flow rate of 1,500 sccm.

[0095] The following steps were performed sequentially: (inject precursor for 20 seconds) - (inject purge gas for 35 seconds) - (inject reaction gas for 5 seconds) - (inject purge gas for 50 seconds), and this constituted one cycle.

[0096] The canister temperature was maintained at 80°C, the process temperature was set to 250°C to 410°C, and the hafnium oxide film was deposited over 100 cycles.

[0097] Manufacturing Example 2: Manufacturing of Hafnium Thin Films Using Atomic Layer Deposition (ALD) 2 Using the hafnium compound (Tris(dimethylamido)(2,5-di-ethyl-1H-pyrrolyl)hafnium) synthesized in Example 3 as a precursor, a hafnium oxide film was produced via atomic layer deposition (ALD).

[0098] The hafnium thin film was deposited under the same conditions as in Production Example 1, except that the precursor injection time was 15 seconds, the purge gas injection time in the first purge step was 15 seconds, and the purge gas injection time in the second purge step was 30 seconds.

[0099] Table 1 below shows the process conditions for manufacturing the thin films in manufacturing examples 1 and 2. [Table 1]

[0100] Manufacturing Example 3: Manufacturing of Zirconium Thin Films Using Atomic Layer Deposition (ALD) Except for using the zirconium compound synthesized in Example 4 (Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl)zirconium) as a precursor and appropriately adjusting some of the process conditions, the zirconium oxide film was produced via atomic layer deposition (ALD) in the same manner as in Production Examples 1 and 2 (using water vapor (H2O) as the reaction gas).

[0101] Furthermore, a zirconium oxide film was produced via atomic layer deposition (ALD) in the same manner as in Production Examples 1 and 2 (using water vapor (H2O) as the reaction gas), with some process conditions being appropriately adjusted, except that the zirconium compound synthesized in Example 5 (Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl)zirconium) was used as a precursor and some process conditions were appropriately adjusted.

[0102] The deposition rates of the thin films produced by Production Example 1 and Production Example 2 were analyzed.

[0103] Evaluation Example 1: Measurement of Vapor Deposition Rate Thin films were manufactured according to the manufacturing example, with the process temperature varied from 250°C to 410°C under the process conditions described in Table 1. The deposition rate per cycle (GPC) of the thin films was measured, and the deposition rate for manufacturing example 1 is shown in Figure 1, and the deposition rate for manufacturing example 2 is shown in Figure 2.

[0104] The deposition rate was calculated using the following formula 1. [Mathematics 1] Evaporation rate (Å / cycle) = Evaporation thickness / Number of ALD cycles

[0105] The deposition thickness in Equation 1 above was measured using an ellipsometer and confirmed using a FE-SEM.

[0106] As shown in Figures 1 and 2, in the case of Production Example 1 using the compound of Example 2, a constant deposition rate (ALD window) is shown at temperatures in the range of 270°C to 330°C, and in the case of Production Example 2 using the compound of Example 3, a constant deposition rate (ALD window) is shown at temperatures in the range of 250°C to 330°C, regardless of the process temperature. This confirms that deposition is possible by atomic layer deposition (ALD) when using the novel precursor compounds for vapor deposition, including the compounds of Example 2 and Example 3, and that Hf metal thin films could be manufactured.

[0107] When the compound from Example 2 was used, the deposition rate (GPC) was between 0.65 and 1.10, and when the compound from Example 3 was used, the deposition rate was between 0.60 and 1.00.

[0108] Furthermore, as shown in Figures 1 and 2, a section is observed in the temperature range of 330°C to 410°C where the process temperature and the deposition rate increase proportionally. This indicates a behavior similar to that observed when deposition is performed by chemical vapor deposition (CVD). Therefore, it has been confirmed that the precursor composition of this application can also be used in chemical vapor deposition (CVD).

[0109] We confirmed that when vapor deposition was performed using a vapor deposition precursor composition containing the novel compound Example 1, a hafnium (Hf) metal thin film was deposited in the same manner as in Production Examples 1 and 2.

[0110] Furthermore, it was confirmed that a zirconium (Zr) metal thin film was formed when vapor deposition was carried out using a vapor deposition precursor composition containing the novel compound in Example 4 and a vapor deposition precursor composition containing the novel compound in Example 5.

[0111] Through the thin film manufacturing process described above, it can be seen that when the novel compound of this application is used as a precursor composition for deposition and deposition is performed by ALD, a thin film with excellent properties can be formed, and that deposition by CVD is also possible using the novel compound of this application as a precursor composition.

[0112] The scope of the present invention is expressed more by the claims described below than by the above detailed description, and it should be interpreted that the meaning and scope of the claims, and any modified or altered forms derived therefrom, are included within the scope of the present invention. [Industrial applicability]

[0113] The novel compound and precursor composition containing the novel compound according to the present invention are excellent in reactivity, volatility, and thermal stability, are liquid, and enable uniform thin film deposition with excellent properties, thereby ensuring excellent thin film properties, thickness, and step coverage.

[0114] The physical properties described above provide a precursor suitable for atomic layer deposition and chemical vapor deposition.

Claims

1. The compound represented by the following chemical formula 1: 【Chemistry 1】 In the aforementioned chemical formula 1, M is titanium (Ti), zirconium (Zr), or hafnium (Hf); R 1 ~R 4 Each of these is independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 6 carbon atoms; R 5 ~R 10 These are, independently, hydrogen and a linear or branched hydrocarbon group having 1 to 4 carbon atoms.

2. R 1 ~R 4 The compound according to claim 1, wherein each is independently selected from the group consisting of hydrogen, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group.

3. R 5 ~R 10 The compound according to claim 1, wherein each is independently selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group.

4. The compound according to claim 1, represented by the following chemical formulas 1-1, 1-2, or 1-3. 【Chemistry 1-1】 【Chemistry 1-2】 [Chemistry 1-3] In the aforementioned chemical formulas 1-1, 1-2, and 1-3, M is titanium (Ti), zirconium (Zr), or hafnium (Hf).

5. A precursor composition for vapor deposition comprising the compound described in any one of claims 1 to 4.

6. A method for producing a thin film, comprising the step of introducing the vapor deposition precursor composition described in claim 5 into a chamber.

7. The method for manufacturing the thin film according to claim 6, wherein the method for manufacturing the thin film includes atomic layer deposition (ALD) or chemical vapor deposition (CVD).

8. As a reaction gas, injecting any one or more selected from hydrogen (H 2 ), an oxygen (O) atom-containing compound, a nitrogen (N) atom-containing compound, or a silicon (Si) atom-containing compound; The method for producing a thin film according to claim 6, further comprising the step of

9. The reaction gas is hydrogen (H 2 ), water vapor (H 2 O), oxygen (O 2 ), ozone (O 3 ), nitrogen (N 2 ), ammonia (NH 3 ), hydrazine (N 2 H 4 A method for producing a thin film according to claim 8, wherein the thin film is one or more selected from ), or silane.

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