Novel compound, precursor composition comprising same, and method for manufacturing thin film using same

Abstract

The present invention relates to a vapor deposition compound capable of depositing a thin film through vapor deposition and, more specifically, to: a novel compound that can be applied to atomic layer deposition (ALD) or chemical vapor deposition (CVD) and has excellent reactivity, volatility, and thermal stability; a precursor composition comprising the novel compound; and a method for manufacturing a thin film using the precursor composition.

Description

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

[0001] The present invention relates to a novel compound capable of forming a thin film through vapor deposition, a precursor composition comprising the novel compound, and a method for manufacturing a thin film using the precursor composition.

[0002]

[0003] As semiconductor devices become more highly integrated and miniaturized, it is becoming increasingly important to form metal and metal oxide thin films of uniform thickness for application in various technologies such as microelectronics, magnetic information storage, and catalysts.

[0004] Chemical vapor deposition (CVD) or atomic layer deposition (ALD) are used to manufacture metal and metal oxide thin films. ALD, in particular, enables the formation of desired thin films by sequentially injecting and removing reactants into a chamber, allowing for easy composition control and the formation of films with uniform thickness. Furthermore, ALD offers excellent step coverage, allowing for the uniform growth of thin films on complex and sophisticated devices.

[0005] Precursors play a crucial role in the manufacture of thin films using atomic layer deposition (ALD), requiring high volatility, high thermal stability, and high reactivity within the chamber. To date, precursor development has been conducted using a variety of ligands, with representative ligands known to exist including halogens, alkoxides, cyclopentadienes, beta-diketonates, amides, and amidinates. However, most known precursors are solid compounds, have low volatility or stability, or can cause problems such as impurity contamination during thin film deposition. Therefore, the development of novel precursors with superior properties that overcome the aforementioned shortcomings is required.

[0006] In particular, silicon dioxide (SiO2) has been used as the gate dielectric material for transistors until now. However, as semiconductor devices have become increasingly smaller, problems such as tunneling current leakage and the resulting increased power dissipation and heat generation have become more serious. Therefore, the need to develop new materials with high permittivity to replace SiO2 dielectric has emerged.

[0007] Group IV metals, such as hafnium and zirconium, are widely used as high-k thin-film materials due to their relatively wide bandgap energy, high Si density, and high compatibility. However, existing precursor materials used to produce hafnium or zirconium thin films have limitations in improving the deposition rate, uniformity, flatness, and purity of the thin films, necessitating the development of improved precursors.

[0008] [Prior Art Literature]

[0009] [Patent Document]

[0010] (Patent Document 1) Republic of Korea Publication Patent No. 2011-0065383

[0011] (Patent Document 2) Republic of Korea Publication Patent No. 2014-0029428

[0012] The present invention aims to provide a novel compound containing a Group 4 metal element applicable to atomic layer deposition (ALD) or chemical vapor deposition (CVD) and a precursor composition containing the same.

[0013] In particular, the purpose is to provide a precursor composition that is liquid, can be purified at low temperatures, has excellent thermal stability and volatility, and can be deposited as a thin film over a wide temperature range.

[0014] In addition, the present invention seeks to provide a method for manufacturing a thin film using the precursor composition.

[0015] However, the problems that the present invention seeks to solve are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

[0016] In one aspect, the present invention provides a compound represented by the following chemical formula 1:

[0017] [Chemical Formula 1]

[0018]

[0019] In the above chemical formula 1,

[0020] M is titanium (Ti), zirconium (Zr), or hafnium (Hf);

[0021] R1 to R4 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms;

[0022] R5 to R 10 are, each independently, hydrogen and a linear or branched hydrocarbon group having 1 to 4 carbon atoms.

[0023]

[0024] Another aspect of the present invention provides a precursor composition for vapor deposition comprising the compound.

[0025]

[0026] Another aspect of the present invention provides a method for manufacturing a thin film, comprising the step of introducing the precursor composition for vapor deposition into a chamber.

[0027] The novel compound according to the present invention and the precursor composition comprising the novel compound have excellent 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.

[0028] The above properties provide a precursor suitable for atomic layer deposition and chemical vapor deposition.

[0029] Figure 1 is a graph showing the change in deposition rate according to the change in process temperature of the Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl) hafnium compound of Example 2 of the present invention.

[0030] Figure 2 is a graph showing the change in deposition rate according to the change in process temperature of the Tris(dimethylamido)(2,5-di-ethyl-1H-pyrrolyl) hafnium compound of Example 3 of the present invention.

[0031] Hereinafter, the functions and effects of the invention will be described in more detail through specific examples. However, these examples are provided merely as examples of the invention and do not define the scope of the invention.

[0032] Prior to this, the terms or words used in this specification and claims should not be interpreted as limited to their usual or dictionary meanings, and should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0033] Accordingly, the configuration of the embodiments described in this specification is only one of the most preferred embodiments of the present invention and does not represent all of the technical ideas of the present invention, so it should be understood that various equivalents and modified examples that can replace them may exist at the time of filing this application.

[0034] In this specification, singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "comprise," "include," or "have" should be understood to indicate the presence of a feature, number, step, component, or combination thereof, but not to preclude the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0035] In this specification, “a to b” and “a~b” indicating a numerical range are defined as “a to” and “~” as ≥a and ≤b.

[0036]

[0037] A compound according to one aspect of the present invention may be represented by the following chemical formula 1.

[0038] [Chemical Formula 1]

[0039]

[0040] In the above chemical formula 1,

[0041] M is titanium (Ti), zirconium (Zr), or hafnium (Hf);

[0042] R1 to R4 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms;

[0043] R5 to R 10 are, each independently, hydrogen and a linear or branched hydrocarbon group having 1 to 4 carbon atoms.

[0044]

[0045] In one embodiment of the present invention, preferably, R1 to R4 may each independently be any one 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, a tert-butyl group, an n-pentyl group, an iso-pentyl group, a neo-pentyl group, a sec-pentyl group, a tert-pentyl group, a hexyl group, an isohexyl group, and isomers thereof.

[0046] 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 is not limited thereto.

[0047] More preferably, R1 and R4 may be an ethyl group, an iso-propyl group, or a tert-butyl group, and R2 and R3 may be hydrogen. In the case of a compound having a hydrocarbon group other than the above hydrocarbon group, the compound may be in a solid state rather than a liquid state, or its thermal stability may be lower than that of the compound of the present disclosure.

[0048] In one embodiment of the present invention, preferably R5 to R 10 Each of the silver groups may be 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.

[0049] R5 to R 10 More preferably, each independently may be any one 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.

[0050] More preferably, R5 to R 10, each independently, may be an ethyl group or a methyl group. In the case of a compound having a hydrocarbon group other than the above hydrocarbon group, the compound may be in a solid state rather than a liquid state, or its thermal stability may be lower than that of the compound of the present invention.

[0051]

[0052] In one embodiment of the present invention, the chemical formula 1 may be represented by the following chemical formula 1-1, 1-2, or 1-3.

[0053]

[0054] [Chemical Formula 1-1]

[0055]

[0056]

[0057] [Chemical Formula 1-2]

[0058]

[0059]

[0060] [Chemical Formula 1-3]

[0061]

[0062]

[0063] In the above chemical formulas 1-1, 1-2, and 1-3, M is titanium (Ti), zirconium (Zr), or hafnium (Hf).

[0064] That is, examples of the M(Pyrrole)(Amide) compound represented by the above chemical formula 1 may include, but are not limited to, the following hafnium compounds and zirconium compounds:

[0065] Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl)hafnium;

[0066] Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl)hafnium;

[0067] Tris(dimethylamido)(2,5-di-ethyl-1H-pyrrolyl) hafnium;

[0068] Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl) zirconium;

[0069] Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl) zirconium.

[0070]

[0071] In one embodiment of the present invention, the compound represented by Chemical Formula 1 may be liquid at room temperature. In addition, the compound represented by Chemical Formula 1 has a low melting point and excellent volatility at low temperatures.

[0072]

[0073] A precursor composition for vapor deposition according to one aspect of the present invention may include any one of the compounds represented by the above chemical formula 1.

[0074]

[0075] A method for manufacturing a thin film according to one aspect of the present invention may include a step of introducing the precursor composition for vapor deposition into a chamber.

[0076]

[0077] In one embodiment of the present invention, the step of introducing the precursor composition for vapor deposition into the chamber may include a step of physical adsorption, chemical adsorption, or physical and chemical adsorption.

[0078]

[0079] 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).

[0080] 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.

[0081] The method for manufacturing the above thin film may preferably be atomic layer deposition, but is not limited thereto.

[0082] In atomic layer deposition (ALD), the reactants must be highly volatile, stable, and highly reactive. ALD is a method in which reactant materials are supplied separately, and a thin film less than a monolayer is grown through surface reaction during a single deposition cycle. The ligands of the reactant materials adsorbed on the substrate are removed through a chemical reaction with other reactant materials supplied later. When heating the precursor compounds, which are reactants for ALD, in a liquid state can be much more advantageous in terms of reaction speed and process efficiency than in a solid state.

[0083]

[0084] In one embodiment of the present invention, the method for manufacturing the thin film may further include a step of injecting at least one reaction gas selected from among hydrogen (H2), an oxygen (O) atom-containing compound (or mixture), a nitrogen (N) atom-containing compound (or mixture), and a silicon (Si) atom-containing compound (or mixture).

[0085] Specifically, one or more selected from hydrogen (H2), water vapor (H2O), oxygen (O2), ozone (O3), nitrogen (N2), ammonia (NH3), hydrazine (N2H4), or silane may be used as the reaction gas, but is not limited thereto.

[0086] More specifically, water vapor (H2O), oxygen (O2), and ozone (O3) can be used as reaction gases to deposit oxide thin films, and nitrogen (N2), ammonia (NH3), or hydrazine (N2H4) can be used as reaction gases to deposit nitride thin films. In addition, hydrogen (H2) can be used as reaction gases to deposit metal thin films, and silane compounds can be used.

[0087] Preferably, water vapor (H2O), oxygen (O2), ozone (O3), or a combination thereof can be used as a reaction gas to deposit an oxide thin film.

[0088]

[0089] In one embodiment of the present invention, when the method for manufacturing the thin film is atomic layer deposition (ALD), the method may include a first purge step of purging the precursor composition from the chamber before the step of injecting the reaction gas, and / or a second purge step of purging byproducts that do not react with the precursor composition or are generated by reacting with the precursor composition after the step of injecting the reaction gas.

[0090] The above purge step helps the precursor move on the substrate, ensures that the inside of the reactor has an appropriate pressure for deposition, and also releases impurities present inside the reactor to the outside. That is, a process of purging the inside of the reactor with an inert gas such as argon (Ar), nitrogen (N2), or helium (He) before and after the supply of the reaction gas may be additionally performed.

[0091]

[0092] 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.

[0093] For example, the process temperature may be 150°C or more and 480°C or less, 200°C or more and 460°C or less, or 230°C or more and 440°C or less. The process temperature may preferably be 250°C or more and 410°C or less.

[0094]

[0095] In one embodiment of the present invention, the method for manufacturing the thin film may have a canister temperature of -20°C or higher and 110°C or lower.

[0096] For example, the canister temperature may be 0°C or more and 105°C or less, 20°C or more and 100°C or less, 40°C or more and 95°C or less, 60°C or more and 90°C or less, 70°C or more and 80°C or less, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C. The canister temperature may preferably be 80°C.

[0097] A canister is used to supply a source gas into a chamber for reaction in a thin film manufacturing method. Typically, the canister vaporizes a precursor composition to generate a source gas, which is then supplied into the chamber.

[0098] When the canister temperature is lower than -20°C or higher than 110°C, the uniformity of the thickness of the thin film manufactured through the above-described thin film manufacturing method may be significantly reduced. This is because, when the canister temperature is lower than -20°C, the amount of precursor composition supplied to the chamber is insufficient, and when the canister temperature is higher than 110°C, it may be difficult to obtain a uniform film quality due to deterioration caused by thermal energy or excessive supply of the precursor composition to the chamber.

[0099]

[0100] 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 carrier gas may be 10 sccm or more and 1000 sccm or less.

[0101] For example, the precursor composition injection time may be 1 second or more and 29 seconds or less, 4 seconds or more and 27 seconds or less, 7 seconds or more and 25 seconds or less, 10 seconds or more and 23 seconds or less, 13 seconds or more and 21 seconds or less, or 15 seconds or more and 20 seconds or less.

[0102] The purge gas injection amount of the first purge step may be 20 sccm or more and 800 sccm or less, 40 sccm or more and 700 sccm or less, 60 sccm or more and 600 sccm or less, 80 sccm or more and 500 sccm or less, 100 sccm or more and 450 sccm or less, 150 sccm or more and 400 sccm or less, or 250 sccm or more and 350 sccm or less.

[0103] If the process is performed beyond or below the above range, it may be difficult to form an appropriate thin film.

[0104] Specifically, if the injection time of the precursor composition is less than 1 second, the reactants necessary for forming the thin film may be insufficient, preventing the formation of a thin film of an appropriate thickness. On the other hand, if the injection time of the precursor composition exceeds 30 seconds, the composition ratio of the thin film produced may become inconsistent due to impurities resulting from residual compounds after the reaction.

[0105] In addition, if the injection amount of the precursor composition carrier gas is less than 10 sccm, the residual amount of the precursor composition as a reactant may increase, causing an improper reaction, and impurities may not be purged, causing the thin film layer to be deposited unevenly.

[0106]

[0107] 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 amount of the reaction gas may be 50 sccm or more and 3000 sccm or less.

[0108] For example, the injection time of the reaction gas may be 2 seconds or more and 25 seconds or less, 2 seconds or more and 20 seconds or less, 3 seconds or more and 15 seconds or less, or 3 seconds or more and 10 seconds or less. The injection time of the reaction gas may preferably be 3 seconds or more and 7 seconds or less.

[0109] In addition, the reaction gas injection amount 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.

[0110] In addition, if the injection amount of the reaction gas is less than 50 sccm, the residual amount of the precursor composition, which is the reactant, may increase, resulting in an improper reaction and the generation of impurities, which may cause the thin film layer to be deposited unevenly. On the other hand, if the injection amount of the reaction gas exceeds 3000 sccm, impurities due to the reaction gas compound may be generated.

[0111]

[0112] 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 purge gas injection amounts of the first purge step and the second purge step may each independently be 100 sccm or more and 2000 sccm or less.

[0113] For example, the purge gas injection time of 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 or less, and the purge gas injection time of 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 or less.

[0114] The purge gas injection amounts of the first purge step and the second purge step are each independently 100 sccm or more and 200 sccm or less, 100 sccm or more and 300 sccm or less, 100 sccm or more and 400 sccm or less, 100 sccm or more and 500 sccm or less, 100 sccm or more and 600 sccm or less, 100 sccm or more and 700 sccm or less, 100 sccm or more and 800 sccm or less, 100 sccm or more and 900 sccm or less, 100 sccm or more and 1000 sccm or less, 100 sccm or more and 1200 sccm or less, 100 sccm or more and 1400 sccm or less, 100 sccm or more and 1600 sccm or less, 100 sccm or more and 1800 sccm or less, 200 sccm or more and 1700 sccm or less, and 300 sccm or more. It may be 1600 sccm or less, 400 sccm or more but 1600 sccm or less, 500 sccm or more but 1600 sccm or less, 600 sccm or more but 1600 sccm or less, 700 sccm or more but 1600 sccm or less, 800 sccm or more but 1600 sccm or less, or 900 sccm or more but 1600 sccm or less.

[0115]

[0116] In one embodiment of the present invention, the number of repetitions of the cycle may be 10 or more.

[0117] For example, the number of repetitions of the above 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, 100,000 or more, and 1,000,000 or less.

[0118]

[0119] If the process conditions for the above-described reaction gas, process temperature, precursor composition, and purge gas are not satisfied, a thin film with excellent properties cannot be obtained.

[0120]

[0121] Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples.

[0122]

[0123] [Synthesis example]

[0124] Synthesis Example 1: Synthesis of 2,2,7,7-tetramethyloctane-3,6-dione

[0125] Potassium hydride (in THF) was added to a flask, and 3,3-dimethylbutan-2-one was slowly added at 0°C and stirred for 1 hour. Then, copper(II) chloride (CuCl2) (in DMF) was slowly added at -78°C, stirred for 3 hours at 60°C, and then stirred for 24 hours at room temperature. After lowering the flask temperature and adding 1 M HCl to react (work up), diethyl ether, water (H2O), and brine were added to extract the compound. The extracted compound was dried using MgSO4, filtered, and concentrated under reduced pressure to obtain 2,2,7,7-tetramethyloctane-3,6-dione.

[0126] The chemical structure and NMR measurement results of the obtained 2,2,7,7-tetramethyloctane-3,6-dione are as follows.

[0127]

[0128] [Chemical structure of 2,2,7,7-tetramethyloctane-3,6-dione]

[0129]

[0130] 1 H-NMR (400MHz, CDCl3):

[0131] δ 1.17 (s, 9H), 2.76 (s, 2H)

[0132]

[0133] Synthesis Example 2: Synthesis of 2,5-di-tert-butyl-1H-pyrrole ligand

[0134] 2,2,7,7-Tetramethyloctane-3,6-dione, acetic acid, and ammonium acetate obtained in Synthetic Example 1 were added to a flask and stirred at 100°C for 4 hours. After stirring, an aqueous potassium carbonate solution was slowly added to the compound, and the compound was extracted using diethyl ether, deionized water (DIW), and brine. The extracted compound was dried using MgSO4, and the filtrate was secured through a filter, concentrated under reduced pressure, and then purified. The synthesized 2,5-di-tertbutyl-1H-pyrrole was a transparent liquid compound, and the synthetic yield was 55%.

[0135] The chemical structure and NMR measurement results of the synthesized 2,5-di-tert-butyl-1H-pyrrole are as follows.

[0136]

[0137] [Chemical structure of 2,5-di-tert-butyl-1H-pyrrole]

[0138]

[0139] 1 H-NMR (400MHz, CDCl3):

[0140] δ 1.30 (s, 9H), 5.8 (d, 2H)

[0141]

[0142] Synthesis Example 3: Synthesis of 2,7-dimethyloctane-3,6-dione

[0143] Potassium hydride (in THF) was added to a flask, and 3-methylbutan-2-one was slowly added at 0 ℃ and stirred for 1 hour. Then, copper(II) chloride (CuCl2) (in DMF) was slowly added at -78 ℃ and stirred at room temperature for 24 hours. After lowering the flask temperature and adding 1 M HCl to react (work up), diethyl ether, water (H2O), and brine were added to extract the compound. The extracted compound was dried using MgSO4, and the filter filtrate was secured through a filter and concentrated under reduced pressure to obtain 2,7-dimethyloctane-3,6-dione.

[0144] The chemical structure and NMR measurement results of the obtained 2,7-dimethyloctane-3,6-dione are as follows.

[0145]

[0146] [Chemical structure of 2,7-dimethyloctane-3,6-dione]

[0147]

[0148] 1 H-NMR (400MHz, CDCl3):

[0149] δ 1.1(d, 12H), 2.6(m, 2H), 2.7(s, 4H)

[0150]

[0151] Synthesis Example 4: Synthesis of 2,5-di-isopropyl-1H-pyrrole ligand

[0152] 2,7-Dimethyloctane-3,6-dione, acetic acid, and ammonium acetate obtained in Synthetic Example 3 were added to a flask and stirred at 100°C for 4 hours. After stirring, an aqueous potassium carbonate solution was slowly added to the compound, and the compound was extracted using diethyl ether, deionized water (DIW), and brine. The extracted compound was dried using MgSO4, and the filtrate was secured through a filter, concentrated under reduced pressure, and then purified. The synthesized 2,5-di-isopropyl-1H-pyrrole was a transparent liquid compound with a synthetic yield of 30%.

[0153] The chemical structure and NMR measurement results of the synthesized 2,5-di-isopropyl-1H-pyrrole are as follows.

[0154]

[0155] [Chemical structure of 2,5-di-isopropyl-1H-pyrrole]

[0156]

[0157] 1 H-NMR (400MHz, CDCl3):

[0158] δ 1.4(d, 12H), 2.9(m, 2H), 5.8(s, 2H)

[0159]

[0160] Synthesis Example 5: Synthesis of octane-3,6-dione

[0161] Nitroalkane and potassium carbonate were added to a flask, dissolved in water, and stirred at room temperature for 5 minutes. Enone was then added, stirred at room temperature for 3 hours, and 30% hydrogen peroxide was added, stirred at room temperature. Diethyl ether, water (H2O), and brine were added, worked up, and dried using MgSO4. The filtrate was filtered and concentrated under reduced pressure to obtain octane-3,6-dione.

[0162] The chemical structure and NMR measurement results of the obtained octane-3,6-dione are as follows.

[0163]

[0164] [Chemical structure of octane-3,6-dione]

[0165]

[0166] 1 H-NMR (400MHz, CDCl3):

[0167] δ 1.10(t, 6H), 2.50(q, 4H), 2.70(s, 4H)

[0168]

[0169] Synthesis Example 6: Synthesis of 2,5-di-ethyl-1H-pyrrole ligand

[0170] Octane-3,6-dione, acetic acid, and ammonium acetate obtained in Synthetic Example 5 were added to a flask and stirred at 100°C for 4 hours. After stirring, an aqueous potassium carbonate solution was slowly added to the compound, and the compound was extracted using diethyl ether, deionized water (DIW), and brine. The extracted compound was dried using MgSO4, and the filtrate was secured through a filter, concentrated under reduced pressure, and then purified. The synthesized 2,5-di-ethyl-1H-pyrrole was a transparent liquid compound with a synthetic yield of 70%.

[0171] The chemical structure and NMR measurement results of the synthesized 2,5-di-ethyl-1H-pyrrole are as follows.

[0172]

[0173] [Chemical structure of 2,5-di-ethyl-1H-pyrrole]

[0174]

[0175] 1 H-NMR (400MHz, CDCl3):

[0176] δ 1.3(t, 6H), 2.6(q, 4H), 2.7(s, 2H)

[0177]

[0178] [Example]

[0179] Example 1: Preparation of Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl) hafnium

[0180] Tetrakis(dimethylamido)hafnium (TDMAH) was placed in a flask and diluted with toluene. The temperature was 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 was added, the mixture was stirred at room temperature for 24 hours. Then, the solvent was concentrated under reduced pressure to secure the compound, and Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl) hafnium was obtained through purified under reduced pressure. The synthesized Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl) hafnium was a red liquid compound with a synthetic yield of 40%.

[0181]

[0182] The chemical structure and NMR measurement results of the synthesized Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl) hafnium are as follows.

[0183]

[0184] [Chemical structural formula of Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl) hafnium]

[0185]

[0186] 1 H-NMR (400MHz, C6D6):

[0187] δ 1.40(s, 18H), 2.98(s, 18H), 6.20(s, 2H)

[0188]

[0189] Example 2: Preparation of Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl) hafnium

[0190] Tetrakis(dimethylamido)hafnium (TDMAH) was placed in a flask and diluted with toluene. The temperature was lowered to 0 ℃, and 2,5-di-isopropyl-1H-pyrrole (Synthesis Example 4) diluted in toluene was slowly added while stirring. After all was added, the mixture was stirred at room temperature for 24 hours. Then, the solvent was concentrated under reduced pressure to secure the compound, and Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl) hafnium was obtained through purified under reduced pressure. The synthesized Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl) hafnium was a yellow liquid compound, and the synthetic yield was 50%.

[0191]

[0192] The chemical structure and NMR measurement results of the synthesized Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl) hafnium are as follows.

[0193]

[0194] [Chemical structural formula of Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl) hafnium]

[0195]

[0196] 1 H-NMR (400MHz, C6D6):

[0197] δ 1.35(d, 12H), 2.98(s, 18H), 3.09(m, 2H), 6.18(s,2H)

[0198]

[0199] Example 3: Preparation of Tris(dimethylamido)(2,5-di-ethyl-1H-pyrrolyl) hafnium

[0200] Tetrakis(dimethylamido)hafnium (TDMAH) was placed in a flask and diluted with toluene. The temperature was lowered to 0 ℃, and 2,5-di-ethyl-1H-pyrrole (Synthesis Example 6) diluted in toluene was slowly added while stirring. After all was added, the mixture was stirred at room temperature for 24 hours. Then, the solvent was concentrated under reduced pressure to secure the compound, and Tris(dimethylamido)(2,5-di-ethyl-1H-pyrrolyl) hafnium was obtained through purified under reduced pressure. The synthesized Tris(dimethylamido)(2,5-di-ethyl-1H-pyrrolyl) hafnium was a yellow liquid compound, and the synthetic yield was 50%.

[0201]

[0202] The chemical structure and NMR measurement results of the synthesized Tris(dimethylamido)(2,5-di-ethyl-1H-pyrrolyl) hafnium are as follows.

[0203]

[0204] [Chemical structural formula of Tris(dimethylamido)(2,5-di-ethyl-1H-pyrrolyl) hafnium]

[0205]

[0206] 1 H-NMR (400MHz, C6D6):

[0207] δ 1.3(t, 6H), 2.7(q, 4H), 2.9(s, 18H), 6.1(s, 2H)

[0208]

[0209] Example 4: Preparation of Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl) zirconium

[0210] Tetrakis(dimethylamido)zirconium (TDMAZ) was placed in a flask and diluted with toluene. The temperature was lowered to 0 ℃, and 2,5-di-tert-butyl-1H-pyrrole (Synthesis Example 2) diluted in toluene was slowly added while stirring. After all was added, the mixture was stirred at room temperature for 24 hours. Then, the solvent was concentrated under reduced pressure to secure the compound, and Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl) zirconium was obtained through purified under reduced pressure. The synthesized Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl) zirconium was a red liquid compound with a synthetic yield of 38%.

[0211]

[0212] The chemical structure and NMR measurement results of the synthesized Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl) zirconium are as follows.

[0213]

[0214] [Chemical structural formula of Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl) zirconium]

[0215]

[0216] 1 H-NMR (400MHz, C6D6):

[0217] δ 1.40(s, 18H), 2.96(s, 18H), 6.19(s, 2H)

[0218]

[0219] Example 5: Preparation of Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl) zirconium

[0220] Tetrakis(dimethylamido)zirconium (TDMAZ) was placed in a flask and diluted with toluene. The temperature was lowered to 0 ℃, and 2,5-di-isopropyl-1H-pyrrole (Synthesis Example 4) diluted in toluene was slowly added while stirring. After all was added, the mixture was stirred at room temperature for 24 hours. Then, the solvent was concentrated under reduced pressure to secure the compound, and Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl) zirconium was obtained through purified under reduced pressure. The synthesized Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl) zirconium was a yellow liquid compound, and the synthetic yield was 51%.

[0221]

[0222] The chemical structure and NMR measurement results of the synthesized Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl) zirconium are as follows.

[0223]

[0224] [Chemical structural formula of Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl) zirconium]

[0225]

[0226] 1 H-NMR (400MHz, C6D6):

[0227] δ 1.34(d, 12H), 2.97(s, 18H), 3.05(m, 2H), 6.16(s,2H)

[0228]

[0229] [Manufacturing example]

[0230] Manufacturing Example 1: Manufacturing of a hafnium thin film using atomic layer deposition (ALD) 1

[0231] A hafnium thin film was manufactured through atomic layer deposition (ALD) using the hafnium compound (Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl) hafnium) synthesized in Example 2 as a precursor.

[0232] The substrate used in this experiment was a p-type Si wafer with a resistivity of 0.02 Ω·cm. Prior to deposition, the p-type Si wafer was ultrasonically cleaned in acetone, ethanol, and deionized water (DI water) for 10 minutes each. The native oxide film on the Si wafer was removed after immersing it in a 10% HF solution (HF:H2O=1:9) for 10 seconds. The HF-cleaned Si wafer was immediately transferred to the atomic layer deposition (ALD) chamber.

[0233] Water vapor (H2O) was used as the reaction gas, and was injected at a flow rate of 1,000 sccm by controlling the on / off of the pneumatic valve. Argon (Ar), an inert gas, was used to purge the precursor compound and reaction gas, and the flow rate was set to 1,500 sccm.

[0234] (Precursor injection for 20 seconds) - (Purge gas injection for 35 seconds) - (Reactant gas injection for 5 seconds) - (Purge gas injection for 50 seconds) were performed sequentially, and this was considered one cycle.

[0235] The temperature of the canister was maintained at 80°C, the process temperature was set to 250°C to 410°C, and the number of cycles was 100 to deposit a hafnium oxide film.

[0236]

[0237] Manufacturing Example 2: Manufacturing of a hafnium thin film using atomic layer deposition (ALD) 2

[0238] A hafnium oxide film was manufactured through atomic layer deposition (ALD) using the hafnium compound (Tris(dimethylamido)(2,5-di-ethyl-1H-pyrrolyl) hafnium) synthesized in Example 3 as a precursor.

[0239] A hafnium thin film was deposited under the same conditions as in Manufacturing Example 1, except that the precursor injection time was 15 seconds, the purge gas injection time of the first purge stage was 15 seconds, and the purge gas injection time of the second purge stage was 30 seconds.

[0240]

[0241] The process conditions for manufacturing thin films of Manufacturing Examples 1 and 2 are shown in Table 1 below.

[0242] Canister temperature (℃) Process temperature (℃) Precursor injection time (sec (s)) First purge time (sec (s)) Reactant gas injection time (sec (s)) Second purge time (sec (s)) ALDCycle (times) Manufacturing example 180 250 ~ 410 20 35 550 100 Manufacturing example 280 250 ~ 410 15 15 5 30 100

[0243]

[0244] Manufacturing Example 3: Manufacturing of a zirconium thin film using atomic layer deposition (ALD)

[0245] A zirconium oxide film was manufactured through atomic layer deposition (ALD) in the same manner as in Manufacturing Examples 1 and 2 (using water vapor (H2O) as a reaction gas), except that some process conditions were appropriately adjusted using the zirconium compound (Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl) zirconium) synthesized in Example 4 as a precursor.

[0246] In addition, a zirconium oxide film was manufactured through atomic layer deposition (ALD) by appropriately adjusting some process conditions (using water vapor (H2O) as a reaction gas) in the same manner as in Manufacturing Examples 1 and 2, except that some process conditions were appropriately adjusted using the zirconium compound (Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl) zirconium) synthesized in Example 5 as a precursor.

[0247]

[0248] The deposition rates of the thin film manufactured by the above Manufacturing Example 1 and the thin film manufactured by the above Manufacturing Example 2 were analyzed.

[0249]

[0250] Evaluation Example 1: Deposition Rate Measurement

[0251] In the process conditions described in Table 1 above, the process temperature was changed in the range of 250 ℃ to 410 ℃, and a thin film was manufactured according to the above manufacturing example, and the deposition rate (Growth rate per cycle, GPC) of the thin film was measured. The deposition rate of Manufacturing Example 1 is shown in Figure 1, and the deposition rate of Manufacturing Example 2 is shown in Figure 2.

[0252]

[0253] The deposition rate was calculated using the following mathematical formula 1.

[0254]

[0255] [Mathematical Formula 1]

[0256] Deposition rate (Å / cycle) = deposition thickness / number of ALD cycles

[0257] The deposition thickness of the above mathematical expression 1 was measured using an ellipsometer and confirmed using FE-SEM.

[0258]

[0259] As shown in FIGS. 1 and 2, in the case of Manufacturing Example 1 using the compound of Example 2, a section (ALD window) in which the deposition rate is constant regardless of the process temperature is shown at a temperature range of 270°C to 330°C, and in the case of Manufacturing Example 2 using the compound of Example 3, a section in which the deposition rate is constant is shown at a temperature range of 250°C to 330°C. Therefore, it was confirmed that deposition was possible by the atomic layer deposition (ALD) method when precursor compounds for vapor deposition including the novel compounds of Examples 2 and 3 were used, and a Hf metal thin film could be manufactured.

[0260] When the compound of Example 2 was used, it was confirmed that the deposition rate (Growth rate per cycle, GPC) was 0.65 or more and 1.10 or less, and when the compound of Example 3 was used, the deposition rate was 0.60 or more and 1.00 or less.

[0261] In addition, as shown in FIGS. 1 and 2, a section in which the process temperature and deposition rate increase proportionally in the temperature range of 330°C to 410°C was observed, which confirmed that a similar pattern was observed as that deposited by chemical vapor deposition (CVD). Therefore, it was confirmed that the precursor composition of the present disclosure can also be used in chemical vapor deposition (CVD).

[0262] It was confirmed that a hafnium (Hf) metal thin film was deposited using a precursor composition for vapor deposition including the novel compound, Example 1, as in the cases of Manufacturing Examples 1 and 2.

[0263] In addition, it was confirmed that a zirconium (Zr) metal thin film was formed when a vapor deposition precursor composition including the novel compound Example 4 and a vapor deposition precursor composition including the novel compound Example 5 were used for deposition.

[0264]

[0265] Through the above thin film manufacturing, it was found that a thin film with excellent properties can be formed when the novel compound of the present invention is used as a precursor composition for deposition and deposition by ALD is performed, and that deposition by CVD is also possible using the novel compound of the present invention as a precursor composition for deposition.

[0266]

[0267] The scope of the present invention is indicated by the claims described below rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

[0268]

[0269] The novel compound according to the present invention and the precursor composition comprising the novel compound have excellent 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.

[0270] The above properties provide a precursor suitable for atomic layer deposition and chemical vapor deposition.

Claims

1. A compound represented by the following chemical formula 1: [Chemical Formula 1] 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.

2. In paragraph 1, A compound wherein R1 to R4 are each independently one 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. In paragraph 1, R5 to R 10 A compound, each independently selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group.

4. In paragraph 1, Represented by the following chemical formula 1-1, 1-2, or 1-3, compound. [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] In the above chemical formulas 1-1, 1-2 and 1-3, M is titanium (Ti), zirconium (Zr), or hafnium (Hf).

5. Comprising a compound according to any one of paragraphs 1 to 4, A precursor composition for vapor deposition.

6. A step of introducing a precursor composition for vapor deposition according to Article 5 into a chamber, Method for manufacturing thin films.

7. In paragraph 6, The method for manufacturing the above thin film includes atomic layer deposition (ALD) or chemical vapor deposition (CVD).

8. In paragraph 6, Further comprising a step of injecting at least one selected from a compound containing hydrogen (H2), an oxygen (O) atom, a compound containing nitrogen (N) atom, or a compound containing silicon (Si) atom as a reaction gas. Method for manufacturing thin films.

9. In paragraph 8, A method for manufacturing a thin film, wherein the above reaction gas is at least one selected from hydrogen (H2), water vapor (H2O), oxygen (O2), ozone (O3), nitrogen (N2), ammonia (NH3), hydrazine (N2H4), or silane.

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