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

Abstract

The present invention relates to a vapor deposition compound capable of depositing a thin film by vapor deposition, and more particularly, to a vapor deposition compound capable of depositing a thin film by vapor deposition, and more particularly, to a vapor deposition compound capable of depositing a thin film by vapor deposition, which can be applied to an atomic layer deposition (ALD) method or a chemical vapor deposition method. The present invention relates to a novel compound having 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 which can be used for thin film deposition by vapor deposition in a gas phase, a precursor composition comprising the novel compound, and a method for manufacturing a thin film using the precursor composition. BACKGROUND

[0002] With the development of high integration and high miniaturization of semiconductor elements, it has become increasingly important to form a metal and metal oxide thin film of uniform thickness for use in various technologies such as microelectronics, magnetic information storage, catalysts, etc.

[0003] A chemical vapor deposition method (CVD) or an atomic layer deposition method (ALD) is used to manufacture a metal and metal oxide thin film, and in particular, the atomic layer deposition method, which is a method of sequentially injecting a reaction material into the inside of a chamber and removing it, can form a desired thin film, easily adjust the composition, and form a thin film of uniform thickness. In addition, the atomic layer deposition method has excellent step coverage, and thus has the advantage of being able to uniformly grow a thin film on a complex and precise element.

[0004] In order to manufacture a thin film by the atomic layer deposition method, a precursor plays an important role, and is required to have high volatility, high thermal stability, high reactivity in the chamber, etc. So far, various ligands have been applied to the development of a precursor, and representative ligands known to date include halogen, alkoxide, cyclopentadiene, β-diketonate, amide, amidinate, etc. However, most of the known precursors are solid compounds, have low volatility or stability, or can cause problems such as impurity contamination during thin film deposition, and thus there is a need to develop a novel precursor having excellent properties improved from the above-described drawbacks.

[0005] In particular, silicon dioxide (SiO2) has been used as a gate dielectric material for transistors, but as semiconductor element sizes have been continuously reduced in recent years, tunneling current leakage and the resulting increase in power consumption and heat problems have become increasingly serious. Therefore, the necessity of developing a new material having a high dielectric constant to replace the SiO2 dielectric has become increasingly prominent.

[0006] Group 4 metals such as hafnium or zirconium are widely used as high dielectric constant thin film materials due to their relatively wide band gap energy, Si integration, and high interchangeability. However, existing precursor materials for manufacturing hafnium thin films or zirconium thin films have limitations in improving the deposition rate, uniformity, flatness, purity, etc. of the thin film, and thus the development of an improved precursor is imperative.

[0007] [Patent Document]

[0008] [Patent Document]

[0009] (Patent Document 1) Korean Patent Publication No. 2011-0065383

[0010] (Korean Patent Publication No. 2014-0029428) SUMMARY

[0011] PROBLEMS TO BE SOLVED BY THE INVENTION

[0012] The present invention aims to provide a novel Group 4 metal element-containing compound and a precursor composition containing the same, which can be applied to an atomic layer deposition (ALD) method or a chemical vapor deposition (CVD) method.

[0013] In particular, the aim is to provide a precursor composition which is liquid, can be refined at a low temperature, has excellent thermal stability and volatility, and can be used for thin film deposition over a wide temperature range.

[0014] In addition, the present invention aims to provide a thin film manufacturing method using the above-mentioned precursor composition.

[0015] However, the problems to be solved by the present application are not limited by the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art according to the following description.

[0016] METHOD FOR SOLVING THE PROBLEMS

[0017] One aspect of the present application provides a compound represented by the following Chemical Formula 1:

[0018] [Chemical Formula 1]

[0019]

[0020] In the above Chemical Formula 1,

[0021] M is titanium (Ti), zirconium (Zr), or hafnium (Hf);

[0022] R1 to R4 are each independently hydrogen, or a linear or branched hydrocarbon group having 1 to 6 carbon atoms;

[0023] R5 to R 10 are each independently hydrogen, a linear or branched hydrocarbon group having 1 to 4 carbon atoms.

[0024] Another aspect of the present application provides a precursor composition for vapor deposition containing the above-mentioned compound.

[0025] Still another aspect of the present application provides a thin film manufacturing method including the step of introducing the above-mentioned precursor composition for vapor deposition into a chamber.

[0026] EFFECTS OF THE INVENTION

[0027] The novel compound of the present application and the precursor composition containing the same are excellent in reactivity, volatility and thermal stability and are liquid, enabling uniform thin film evaporation of excellent properties, thus ensuring excellent thin film properties, thickness and step coverage.

[0028] The physical properties as described above provide a precursor suitable for atomic layer evaporation method and chemical vapor deposition method. BRIEF DESCRIPTION OF DRAWINGS

[0029] FIG. 1 is a graph showing the variation of the evaporation rate of the tris(dimethylamide)(2,5-diisopropyl-1H-pyrrolyl)hafnium compound of Example 2 of the present application with process temperature.

[0030] FIG. 2 is a graph showing the variation of the evaporation rate of the tris(dimethylamide)(2,5-diethyl-1H-pyrrolyl)hafnium compound of Example 3 of the present application with process temperature. DETAILED DESCRIPTION

[0031] Hereinafter, the effects and advantages of the present application will be described in more detail through specific examples of the present application. However, these examples are provided only as an illustration of the present application, and the scope of the present application is not limited by the examples.

[0032] Prior to this, the terms or words used in the specification and claims of the present application should not be interpreted as limited to the meanings in the generally or dictionary, but should be interpreted based on the concept that the inventors can appropriately define the terms in the best method of explaining their invention, and should be interpreted in accordance with the meanings and concepts in conformity with the technical idea of the present application.

[0033] Therefore, the configuration of the examples described in the present specification is only the most preferred one of the present application, and does not represent all the technical ideas of the present application, and it should be understood that various equivalents and modifications can exist which can replace these examples at the time of filing the present application.

[0034] In the present specification, unless the context clearly indicates otherwise, the singular expression includes the plural expression. In the present specification, it should be understood that the terms such as "comprise", "have" or "include" are intended to designate the existence of the features, numbers, steps, constituent elements or combinations thereof described, and are not intended to preclude the existence or additional possibility of one or more other features, numbers, steps, constituent elements or combinations thereof.

[0035] In the present specification, "to" and "~" in "a to b" and "a~b" indicating a numerical range are defined as ≥a and ≤b.

[0036] The compound of one aspect of the present application can be represented by the following Chemical Formula 1.

[0037] [Chemical Formula 1]

[0038]

[0039] In the above Chemical Formula 1,

[0040] M is titanium (Ti), zirconium (Zr), or hafnium (Hf);

[0041] R1to R4are each independently hydrogen, or a linear or branched hydrocarbon group having 1 to 6 carbon atoms;

[0042] R5to R 10 are each independently hydrogen, a linear or branched hydrocarbon group having 1 to 4 carbon atoms.

[0043] In one embodiment of the present application, preferably, R1to R4may 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 t-butyl group, an n-pentyl group, an iso-pentyl group, a neopentyl group, a sec-pentyl group, a t-pentyl group, a hexyl group, an iso-hexyl group, and isomers thereof.

[0044] R1to R4may 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 t-butyl group, but are not limited thereto.

[0045] More preferably, R1and R4may be an ethyl group, an iso-propyl group, or a t-butyl group, and R2and R3may be hydrogen. If it is a compound having other hydrocarbon groups than the above hydrocarbon groups, it can become a solid compound rather than a liquid, or the thermal stability can be reduced compared to the compound of the present application.

[0046] In one embodiment of the present application, preferably, R5to R 10 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, and a t-butyl group.

[0047] R5to R 10 may each independently 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 are not limited thereto.

[0048] More preferably, R5to R 10 may each independently be an ethyl group or a methyl group. If it is a compound having other hydrocarbon groups than the above hydrocarbon groups, it can become a solid compound rather than a liquid, or the thermal stability can be reduced compared to the compound of the present application.

[0049] In one embodiment of the present application, the above Chemical Formula 1 can be represented by the following Chemical Formulas 1-1, 1-2, or 1-3.

[0050] [Chemical Formula 1-1]

[0051]

[0052] [Chemical Formula 1-2]

[0053]

[0054] [Chemical Formula 1-3]

[0055]

[0056] In the above Chemical Formulas 1-1, 1-2, and 1-3, M is titanium (Ti), zirconium (Zr), or hafnium (Hf).

[0057] That is, as examples of the M(Pyrrole)(Amide) compound represented by the above Chemical Formula 1, there can be the following hafnium compounds and zirconium compounds, but not limited thereto:

[0058] Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl) hafnium;

[0059] Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl) hafnium;

[0060] Tris(dimethylamido)(2,5-di-ethyl-1H-pyrrolyl) hafnium;

[0061] Tris(dimethylamido)(2,5-di-tertbutyl-1H-pyrrolyl) zirconium;

[0062] Tris(dimethylamido)(2,5-di-isopropyl-1H-pyrrolyl) zirconium.

[0063] In one embodiment of the present application, the compound represented by Chemical Formula 1 above can be a liquid at room temperature. In addition, the compound represented by Chemical Formula 1 above has a low melting point and excellent volatility at low temperatures.

[0064] The precursor composition for vapor deposition in one aspect of the present application can include any one of the compounds represented by Chemical Formula 1 above.

[0065] The method for manufacturing a thin film in one aspect of the present application can include the step of introducing the precursor composition for vapor deposition above into a chamber.

[0066] In one embodiment of the present application, the step of introducing the precursor composition for vapor deposition above into a chamber can include the steps of physical adsorption, chemical adsorption, or physical and chemical adsorption.

[0067] In one embodiment of the present application, the method for manufacturing a thin film above can include both Atomic Layer Deposition (ALD) and Chemical Vapor Deposition (CVD).

[0068] More specifically, the vapor deposition method above can 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.

[0069] The method for manufacturing a thin film above can preferably be Atomic Layer Deposition, but is not limited thereto.

[0070] In Atomic Layer Deposition (ALD), the reactants must have high volatility and be stable in substance, and must have high reactivity. Atomic Layer Deposition (ALD) is a method in which reaction materials are separately and supplied, and in one vapor deposition cycle, a monolayer or less of a thin film is grown by surface reaction, and the ligand of the reaction material adsorbed on the substrate is removed by chemical reaction with other reaction materials supplied later. When a precursor compound as a reactant is heated for atomic layer deposition, if it is in a liquid phase, it can be more advantageous than in a solid phase in terms of reaction speed and process.

[0071] In one embodiment of the present application, the method for manufacturing a thin film described above can further include a step of injecting, as a reaction gas, any one or more selected from the group consisting of hydrogen (H2), a compound (or mixture) containing an oxygen (O) atom, a compound (or mixture) containing a nitrogen (N) atom, and a compound (or mixture) containing a silicon (Si) atom.

[0072] Specifically, any one or more selected from the group consisting of hydrogen (H2), water vapor (H2O), oxygen (O2), ozone (O3), nitrogen (N2), ammonia (NH3), hydrazine (N2H4), and silane can be used as the reaction gas, but the present application is not limited thereto.

[0073] More specifically, water vapor (H2O), oxygen (O2), or ozone (O3) can be used as the reaction gas to deposit an oxide thin film, nitrogen (N2), ammonia (NH3), or hydrazine (N2H4) can be used as the reaction gas to deposit a nitride thin film. In addition, hydrogen (H2) can be used as the reaction gas to deposit a metal thin film, and a silane-based compound can be used.

[0074] Preferably, water vapor (H2O), oxygen (O2), ozone (O3), or a combination thereof can be used as the reaction gas to deposit an oxide thin film.

[0075] In one embodiment of the present application, in the case where the method for manufacturing a thin film described above is an atomic layer deposition method (ALD), 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 by-products generated by the reaction with or without the precursor composition after the step of injecting the reaction gas can be included.

[0076] The purge steps described above contribute to the movement of the precursor on the substrate, or make the inside of the reactor have a pressure suitable for deposition, and also discharge impurities and the like present in the reactor to the outside. That is, a process of purifying the inside of the reactor with a non-reactive gas such as argon (Ar), nitrogen (N2), or helium (He) can be further performed before and after the supply of the reaction gas.

[0077] In one embodiment of the present application, the process temperature of the method for manufacturing a thin film described above can be 100°C or higher and 500°C or lower.

[0078] For example, the process temperature described above can be 150°C or higher and 480°C or lower, 200°C or higher and 460°C or lower, 230°C or higher and 440°C or lower. The process temperature described above can preferably be 250°C or higher and 410°C or lower.

[0079] In one embodiment of the present application, the canister temperature of the method for manufacturing a thin film described above can be -20°C or higher and 110°C or lower.

[0080] For example, the tank temperature can 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 tank temperature can preferably be 80°C.

[0081] In the thin film manufacturing method, a tank is used to supply a source gas into a chamber for reaction. Generally, the tank vaporizes a precursor composition to generate a source gas, and then supplies the source gas into the chamber.

[0082] When the tank temperature is lower than -20°C or higher than 110°C, the uniformity of the thickness of the thin film manufactured by the thin film manufacturing method can be significantly reduced. This is because, when lower than -20°C, the amount of the precursor composition supplied into the chamber can be insufficient, and when higher than 110°C, it can be difficult to obtain a uniform film quality due to deterioration by heat energy or excessive supply of the precursor composition into the chamber.

[0083] In one embodiment of the present application, the injection time of the precursor composition can be 1 second or more and 30 seconds or less, and the precursor composition carrier gas injection amount can be 10 seem or more and 1000 seem or less.

[0084] For example, the injection time of the precursor composition can 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, 15 seconds or more and 20 seconds or less,

[0085] The purge gas injection amount of the first purge step can be 20 seem or more and 800 seem or less, 40 seem or more and 700 seem or less, 60 seem or more and 600 seem or less, 80 seem or more and 500 seem or less, 100 seem or more and 450 seem or less, 150 seem or more and 400 seem or less, 250 seem or more and 350 seem or less.

[0086] If the process is performed higher or lower than the above range, it can be difficult to form a proper thin film.

[0087] Specifically, if the injection time of the precursor composition is less than 1 second, it can be difficult to form a thin film of a proper thickness due to insufficient reactants required in the formation of the thin film. On the other hand, if the injection time of the precursor composition is more than 30 seconds, the composition ratio of the manufactured thin film can become inconsistent due to impurities caused by residual compounds after the reaction.

[0088] In addition, if the carrier gas injection amount of the precursor composition is less than 10 seem, the residual amount of the precursor composition as a reactant can increase, an inappropriate reaction can occur, and the film layer can be deposited unevenly due to impurities not being removed.

[0089] In one embodiment of the present application, the injection time of the reaction gas can be 1 second or more and 30 seconds or less, and the injection amount of the reaction gas can be 50 seem or more and 3000 seem or less.

[0090] For example, the injection time of the reaction gas can 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, 3 seconds or more and 10 seconds or less. The injection time of the reaction gas can preferably be 3 seconds or more and 7 seconds or less.

[0091] In addition, the injection amount of the reaction gas can be, for example, 100 seem or more and 2500 seem or less, 300 seem or more and 2000 seem or less, 500 seem or more and 1500 seem or less, 700 seem or more and 1300 seem or less, 900 seem or more and 1100 seem or less.

[0092] In addition, when the injection amount of the reaction gas is less than 50 seem, the residual amount of the precursor composition as a reactant can increase, an inappropriate reaction can occur, and the film layer can be deposited unevenly due to impurities. On the other hand, when the injection amount of the reaction gas is more than 3000 seem, impurities can be generated due to the reaction gas compound.

[0093] In one embodiment of the present application, the injection time of the purge gas of the first purge step can be 1 second or more and 1 minute or less, the injection time of the purge gas of the second purge step can be 10 seconds or more and 1 minute or less, and the injection amount of the purge gas of the first purge step and the second purge step can each independently be 100 seem or more and 2000 seem or less.

[0094] For example, the injection time of the purge gas of the first purge step can 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, 15 seconds or more and 35 seconds or less, and the injection time of the purge gas of the second purge step can be 10 seconds or more and 60 seconds or less, 20 seconds or more and 55 seconds or less, 30 seconds or more and 50 seconds or less,

[0095] The purge gas injection amount of the first purge step and the second purge step can each independently be 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, 300 sccm or more and 1600 sccm or less, 400 sccm or more and 1600 sccm or less, 500 sccm or more and 1600 sccm or less, 600 sccm or more and 1600 sccm or less, 700 sccm or more and 1600 sccm or less, 800 sccm or more and 1600 sccm or less, 900 sccm or more and 1600 sccm or less.

[0096] In one embodiment of the present application, the number of repetitions of the cycle can be 10 or more.

[0097] For example, the number of repetitions of the cycle can 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.

[0098] In a case where the process conditions of the reaction gas, the process temperature, the precursor composition, and the purge gas described above cannot be satisfied, a thin film having excellent properties cannot be obtained.

[0099] Embodiment

[0100] Hereinafter, the present application will be described in more detail by way of examples. However, the following examples are intended to more specifically describe the present application, and the scope of the present application is not limited by the following examples.

[0101] [Synthesis Example]

[0102] Synthesis Example 1: Synthesis of 2,2,7,7-tetramethyloctane-3,6-dione

[0103] In a flask, potassium hydride (THF solution) was added, 3,3-dimethylbutan-2-one was slowly added at 0°C and stirred for 1 hour. Then, copper (II) chloride (CuCl2) (DMF solution) was slowly added at -78°C, and after stirring at 60°C for 3 hours, stirring was performed at normal temperature for 24 hours. After lowering the temperature of the flask, the work up was performed by adding 1M HCl, and diethyl ether, water (H2O) and brine were added to extract the compound. The extracted compound was dried with MgSO4, and then the filtrate was obtained through a filter and concentrated under reduced pressure, thereby obtaining 2,2,7,7-tetramethyloctane-3,6-dione.

[0104] The chemical structural formula of the obtained 2,2,7,7-tetramethyloctane-3,6-dione and the results of NMR measurement are as follows.

[0105] [Chemical structural formula of 2,2,7,7-tetramethyloctane-3,6-dione]

[0106]

[0107] 1 H-NMR (400MHz, CDCl3):

[0108] δ 1.17(s, 9H), 2.76(s, 2H)

[0109] Synthesis Example 2: Synthesis of 2,5-di-tert-butyl-lH-pyrrole ligand

[0110] In a flask, 2,2,7,7-tetramethyloctane-3,6-dione obtained in Synthesis Example 1, acetic acid and ammonium acetate were added, and stirring was performed at 100°C for 4 hours. After completing the stirring, an aqueous solution of potassium carbonate was slowly added to the compound, and the compound was extracted with diethyl ether, deionized water (DIW) and brine. The extracted compound was dried with MgSO4, and then the filtrate was obtained through a filter and refined after concentration under reduced pressure. The synthesized 2,5-di-tertbutyl-1H-pyrrole was a transparent liquid compound, and the synthesis yield was 55%.

[0111] The chemical structure and NMR measurement results of the synthesized 2,5-di-tert-butyl-1H-pyrrole are as follows.

[0112] [Chemical structure of 2,5-di-tert-butyl-1H-pyrrole]

[0113]

[0114] 1 H-NMR (400MHz, CDCl3):

[0115] δ 1.30 (s, 9H), 5.8 (d, 2H)

[0116] Synthesis Example 3: Synthesis of 2,7-dimethyloctane-3,6-dione

[0117] In a flask, potassium hydride (THF solution) was added, 3-methylbutan-2-one was slowly added at 0°C and stirred for 1 hour. Then, copper (II) chloride (CuCl2) (DMF solution) was slowly added at -78°C and stirred at room temperature for 24 hours. After lowering the temperature of the flask, the reaction was treated with 1M HCl, diethyl ether, water (H2O), and brine were added to extract the compound. The extracted compound was dried with MgSO4, then the filtrate was obtained through a filter and concentrated under reduced pressure, thereby obtaining 2,7-dimethyloctane-3,6-dione.

[0118] The chemical structure and NMR measurement results of the obtained 2,7-dimethyloctane-3,6-dione are as follows.

[0119] [Chemical structure of 2,7-dimethyloctane-3,6-dione]

[0120]

[0121] 1 H-NMR (400MHz, CDCl3):

[0122] δ 1.1 (d, 12H), 2.6 (m, 2H), 2.7 (s, 4H)

[0123] Synthesis Example 4: Synthesis of 2,5-diisopropyl-lH-pyrrole ligand

[0124] In a flask, 2,7-dimethyloctane-3,6-dione obtained in Synthesis Example 3, acetic acid, and ammonium acetate were added, and stirred at 100°C for 4 hours. After the stirring was completed, an aqueous solution of potassium carbonate was slowly added to the compound, and the compound was extracted with diethyl ether, deionized water (DIW), and brine. The extracted compound was dried with MgSO4, and then a filtrate was obtained through a filter and concentrated under reduced pressure, followed by purification. The synthesized 2,5-di-isopropyl-lH-pyrrole was a transparent liquid compound, and the synthesis yield was 30%.

[0125] The chemical structural formula of the synthesized 2,5-di-isopropyl-lH-pyrrole and the NMR measurement results are as follows.

[0126] [Chemical structural formula of 2,5-di-isopropyl-lH-pyrrole]

[0127]

[0128] 1 H-NMR (400MHz, CDCI3):

[0129] δ 1.4 (d, 12H), 2.9 (m, 2H), 5.8 (s, 2H)

[0130] Synthesis Example 5: Synthesis of octane-3,6-dione

[0131] In a flask, nitroalkane and potassium carbonate were added, and after being dissolved with water, stirred at room temperature for 5 minutes. Then, enone was added, and stirred at room temperature for 3 hours, and after 30% hydrogen peroxide was added, stirring was performed at room temperature. After the reaction (post-treatment) was performed by adding diethyl ether, water, and brine, drying was performed using MgSO4. Thereafter, a filtrate was obtained through a filter and concentrated under reduced pressure, thereby obtaining octane-3,6-dione.

[0132] The chemical structural formula of the obtained octane-3,6-dione and the NMR measurement results are as follows.

[0133] [Chemical structural formula of octane-3,6-dione]

[0134]

[0135] 1 H-NMR (400MHz, CDC13) :

[0136] δ 1.10 (t, 6H), 2.50 (q, 4H), 2.70 (s, 4H)

[0137] Synthesis Example 6: Synthesis of 2,5-diethyl-lH-pyrrole ligand

[0138] In a flask, octane-3,6-dione obtained in Synthesis Example 5, acetic acid, and ammonium acetate were added, and stirred at 100°C for 4 hours. After the stirring was completed, an aqueous solution of potassium carbonate was slowly added to the compound, and the compound was extracted with diethyl ether, deionized water (DIW), and brine. The extracted compound was dried with MgS04, and then a filtrate was obtained through a filter and refined after being concentrated under reduced pressure. The synthesized 2,5-di-ethyl-lH-pyrrole was a transparent liquid compound, and the synthesis yield was 70%.

[0139] The chemical structural formula of the synthesized 2,5-di-ethyl-lH-pyrrole and NMR measurement results are as follows.

[0140] [Chemical structural formula of 2,5-di-ethyl-lH-pyrrole]

[0141]

[0142] 1 H-NMR (400MHz, CDC13) :

[0143] δ 1.3 (t, 6H), 2.6 (q, 4H), 2.7 (s, 2H)

[0144] [Example]

[0145] Example 1: Production of tris(dimethylamide)(2,5-di-tert-butyl-lH-pyrrolyl)hafnium

[0146] In a flask, tetrakis(dimethylamido)hafnium (TDMAH) was added, diluted with toluene, and the temperature was lowered to 0°C, and then 2,5-diisopropyl-lH-pyrrole (Synthesis Example 4) diluted with toluene was slowly added while stirring. After the entire addition, stirring was performed at normal temperature for 24 hours. Then, the solvent was concentrated under reduced pressure to obtain a compound, and tris(dimethylamido)(2,5-diisopropyl-lH-pyrrolyl)hafnium was obtained by vacuum purification of the obtained compound. The synthesized tris(dimethylamido)(2,5-diisopropyl-lH-pyrrolyl)hafnium was a yellow liquid compound, and the synthesis yield was 50%.

[0147] The chemical formula and NMR measurement results of the synthesized tris(dimethylamido)(2,5-diisopropyl-lH-pyrrolyl)hafnium are as follows.

[0148] [Chemical formula of tris(dimethylamido)(2,5-diisopropyl-lH-pyrrolyl)hafnium]

[0149]

[0150] 1 H-NMR (400MHz, C6D6):

[0151] δ 1.40(s, 18H)、2.98(s, 18H)、6.20(s,2H)

[0152] Example 2: Production of tris(dimethylamide)(2,5-diisopropyl-lH-pyrrolyl)hafnium

[0153] In a flask, tetrakis(dimethylamido)hafnium (TDMAH) was added, diluted with toluene, and the temperature was lowered to 0°C, and then 2,5-diisopropyl-lH-pyrrole (Synthesis Example 4) diluted with toluene was slowly added while stirring. After the entire addition, stirring was performed at normal temperature for 24 hours. Then, the solvent was concentrated under reduced pressure to obtain a compound, and tris(dimethylamido)(2,5-diisopropyl-lH-pyrrolyl)hafnium was obtained by vacuum purification of the obtained compound. The synthesized tris(dimethylamido)(2,5-diisopropyl-lH-pyrrolyl)hafnium was a yellow liquid compound, and the synthesis yield was 50%.

[0154] The chemical formula and NMR measurement results of the synthesized tris(dimethylamido)(2,5-diisopropyl-lH-pyrrolyl)hafnium are as follows.

[0155] [Chemical formula of tris(dimethylamido)(2,5-diisopropyl-lH-pyrrolyl)hafnium]

[0156]

[0157] 1 H-NMR (400MHz, C6D6):

[0158] δ 1.35 (d, 12H), 2.98 (s, 18H), 3.09 (m, 2H), 6.18 (s, 2H)

[0159] Example 3: Production of tris(dimethylamide)(2,5-diethyl-lH-pyrrolyl)hafnium

[0160] In a flask, tetrakis(dimethylamido)hafnium (TDMAH) was added, diluted with toluene, the temperature was lowered to 0°C, and then 2,5-diethyl-lH-pyrrole (synthesis example 6) diluted with toluene was slowly added while stirring. After all of the addition, stirring was performed at normal temperature for 24 hours. Then, the solvent was concentrated under reduced pressure to obtain a compound, and tris(dimethylamido)(2,5-diethyl-lH-pyrrolyl)hafnium was obtained by reduced pressure purification of the obtained compound. The synthesized tris(dimethylamido)(2,5-diethyl-lH-pyrrolyl)hafnium was a yellow liquid compound, and the synthesis yield was 50%.

[0161] The chemical formula and NMR measurement results of the synthesized tris(dimethylamido)(2,5-diethyl-lH-pyrrolyl)hafnium are as follows.

[0162] [Chemical formula of tris(dimethylamido)(2,5-diethyl-lH-pyrrolyl)hafnium]

[0163]

[0164] 1 H-NMR (400MHz, C6D6):

[0165] δ 1.3 (t, 6H), 2.7 (q, 4H), 2.9 (s, 18H), 6.1 (s, 2H)

[0166] Example 4: Production of tris(dimethylamide)(2,5-di-tert-butyl-lH-pyrrolyl)zirconium

[0167] In a flask, tetrakis(dimethylamido)zirconium (TDMAZ) was added, diluted with toluene, and the temperature was lowered to 0°C, and then 2,5-diisopropyl-lH-pyrrole (Synthesis Example 4) diluted with toluene was slowly added while stirring. After the entire addition, stirring was performed at normal temperature for 24 hours. Then, the solvent was concentrated under reduced pressure to obtain a compound, and tris(dimethylamido)(2,5-diisopropyl-lH-pyrrolyl)zirconium was obtained by vacuum purification of the obtained compound. The synthesized tris(dimethylamido)(2,5-diisopropyl-lH-pyrrolyl)zirconium was a yellow liquid compound, and the synthesis yield was 51%.

[0168] The chemical formula and NMR measurement results of the synthesized tris(dimethylamido)(2,5-diisopropyl-lH-pyrrolyl)zirconium are as follows.

[0169] [Chemical formula of tris(dimethylamido)(2,5-diisopropyl-lH-pyrrolyl)zirconium]

[0170]

[0171] 1 H-NMR (400MHz, C6D6):

[0172] δ 1.40(s, 18H)、2.96(s, 18H)、6.19(s,2H)

[0173] Example 5: Production of tris(dimethylamide)(2,5-diisopropyl-lH-pyrrolyl)zirconium

[0174] In a flask, tetrakis(dimethylamido)zirconium (TDMAZ) was added, diluted with toluene, and the temperature was lowered to 0°C, and then 2,5-diisopropyl-lH-pyrrole (Synthesis Example 4) diluted with toluene was slowly added while stirring. After the entire addition, stirring was performed at normal temperature for 24 hours. Then, the solvent was concentrated under reduced pressure to obtain a compound, and tris(dimethylamido)(2,5-diisopropyl-lH-pyrrolyl)zirconium was obtained by vacuum purification of the obtained compound. The synthesized tris(dimethylamido)(2,5-diisopropyl-lH-pyrrolyl)zirconium was a yellow liquid compound, and the synthesis yield was 51%.

[0175] The chemical formula and NMR measurement results of the synthesized tris(dimethylamido)(2,5-diisopropyl-lH-pyrrolyl)zirconium are as follows.

[0176] [Chemical formula of tris(dimethylamido)(2,5-diisopropyl-lH-pyrrolyl)zirconium]

[0177]

[0178] 1 H-NMR (400MHz, C6D6):

[0179] δ 1.34 (d, 12H), 2.97 (s, 18H), 3.05 (m, 2H), 6.16 (s, 2H)

[0180] [Manufacturing Example]

[0181] Production Example 1: Production 1 of hafnium thin film using atomic layer evaporation method (ALD)

[0182] A hafnium compound (tris(dimethylamide)(2,5-diisopropyl-lH-pyrrolyl)hafnium) synthesized in Example 2 was used as a precursor, and a hafnium thin film was manufactured by an atomic layer evaporation method (ALD).

[0183] The substrate used in this experiment was a p-type Si wafer having a resistance of 0.02 Ω-cm. Prior to evaporation, the p-type Si wafer was subjected to an ultra sonic washing in acetone-ethanol-deionized water (DI water) for 10 minutes each. The native oxide thin film on the Si wafer was removed by immersing in a solution of 10% HF (HF:H2O = 1:9) for 10 seconds. The HF-washed Si wafer was immediately transferred to an atomic layer evaporation (ALD) chamber.

[0184] Water vapor (H2O) was used as a reaction gas, and the opening and closing (on / off) of a pneumatic valve was adjusted to be injected at a flow rate of 1,000 seem. For purge of the precursor compound and the reaction gas, argon (Ar) was used as an inactive gas, and the flow rate was set to 1,500 seem.

[0185] The (precursor 20 seconds injection)-(purge gas 35 seconds injection)-(reaction gas 5 seconds injection)-(purge gas 50 seconds injection) was sequentially performed, and this was taken as one cycle.

[0186] 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 set to 100, whereby a hafnium oxide film was evaporated.

[0187] Production Example 2: Production 2 of hafnium thin film using atomic layer evaporation method (ALD)

[0188] A hafnium compound (tris(dimethylamide)(2,5-diethyl-lH-pyrrolyl)hafnium) synthesized in Example 3 was used as a precursor, and a hafnium oxide film was manufactured by an atomic layer evaporation method (ALD).

[0189] A hafnium thin film was deposited under the same conditions as those of Production Example 1 except that the precursor injection time was set to 15 seconds, the purge gas injection time of the first purge step was set to 15 seconds, and the purge gas injection time of the second purge step was set to 30 seconds.

[0190] The process conditions for the thin film production of Production Examples 1 and 2 are shown in Table 1 below.

[0191] [Table 1]

[0192]

[0193] Production Example 3: Production of zirconium thin film using atomic layer evaporation method (ALD)

[0194] A zirconium compound (tris(dimethylamide)(2,5-di-tert-butyl-lH-pyrrolyl)zirconium) synthesized in Example 4 was used as a precursor, and the process conditions were appropriately adjusted, and a zirconium oxide film was produced by an atomic layer deposition method (ALD) (water vapor (H2O) was used as a reaction gas) in the same manner as Production Examples 1 and 2.

[0195] In addition, a zirconium compound (tris(dimethylamide)(2,5-di-tert-butyl-lH-pyrrolyl)zirconium) synthesized in Example 5 was used as a precursor, and the process conditions were appropriately adjusted, and a zirconium oxide film was produced by an atomic layer deposition method (ALD) (water vapor (H2O) was used as a reaction gas) in the same manner as Production Examples 1 and 2.

[0196] The deposition rates of the thin film produced by Production Example 1 and the thin film produced by Production Example 2 were analyzed.

[0197] Evaluation Example 1: Evaporation rate measurement

[0198] The process conditions described in Table 1 above were changed so that the process temperature was in the range of 250°C to 410°C, and thin films were produced according to the above production examples, and the deposition rate (Growth rate per cycle, GPC) of the thin films was measured, and the deposition rate of Production Example 1 was as shown in Table 2 below. FIG. 1 The deposition rate of Production Example 2 was as shown in Table 3 below. FIG. 2

[0199] The deposition rate was calculated by the following Mathematical Formula 1.

[0200] [Mathematical Formula 1]

[0201] Deposition rate (A / cycle) = Deposition thickness / ALD cycle number

[0202] The deposition thickness of the above Mathematical Formula 1 was measured using an ellipsometer (Ellipsometer) and confirmed using an FE-SEM. ​

[0203] As FIG. 1 and FIG. 2 shown, a range of temperatures in which the evaporation rate is constant (ALD window) appears irrespective of the process temperature in the range of 270°C to 330°C in the case of Manufacturing Example 1 using the compound of Example 2, and a range of temperatures in which the evaporation rate is constant (ALD window) appears irrespective of the process temperature in the range of 250°C to 330°C in the case of Manufacturing Example 2 using the compound of Example 3, and it is thus confirmed that, in the case of using the vapor deposition precursor compound containing the novel compound, i.e., the compound of Example 2 and the compound of Example 3, evaporation can be performed by the atomic layer evaporation (ALD) method, and a Hf metal thin film can be produced.

[0204] In the case of using the compound of Example 2, it is confirmed that the growth rate per cycle (GPC) is 0.65 or more and 1.10 or less, and in the case of using the compound of Example 3, it is confirmed that the growth rate per cycle is 0.60 or more and 1.00 or less.

[0205] In addition, as FIG. 1 and FIG. 2 FIG. 1 FIG. 2 shown, a range of temperatures in which the evaporation rate is constant (ALD window) appears irrespective of the process temperature in the range of 270°C to 330°C in the case of Manufacturing Example 1 using the compound of Example 2, and a range of temperatures in which the evaporation rate is constant (ALD window) appears irrespective of the process temperature in the range of 250°C to 330°C in the case of Manufacturing Example 2 using the compound of Example 3, and it is thus confirmed that, in the case of using the vapor deposition precursor compound containing the novel compound, i.e., the compound of Example 2 and the compound of Example 3, evaporation can be performed by the atomic layer evaporation (ALD) method, and a Hf metal thin film can be produced.

[0206] It is confirmed that, in the case of using the vapor deposition precursor composition containing the novel compound of Example 1 as the vapor deposition precursor composition, a hafnium (Hf) metal thin film is also successfully evaporated as in the case of Manufacturing Examples 1 and 2.

[0207] In addition, it is confirmed that, in the case of using the vapor deposition precursor composition containing the novel compound of Example 4 and the vapor deposition precursor composition containing the novel compound of Example 5, a zirconium (Zr) metal thin film is also formed.

[0208] As described above, it is confirmed that, in the case of using the novel compound of the present application as the vapor deposition precursor composition, a thin film having excellent properties can be formed by the ALD-based evaporation, and the novel compound of the present application can also be used as the vapor deposition precursor composition to perform the CVD-based evaporation.

[0209] The scope of the present application is represented by the claims described later, not by the above detailed description, and all modifications or variations of the form derived from the meaning and scope of the claims and equivalent concepts thereof should be interpreted as included in the scope of the present application.

[0210] Industrial Applicability

[0211] The novel compound of the present application and the precursor composition containing the above novel compound are excellent in reactivity, volatility and thermal stability and are liquid, enabling uniform thin film evaporation of excellent properties, thereby enabling excellent thin film properties, thickness and step coverage to be ensured.

[0212] The properties as described above provide a precursor suitable for atomic layer evaporation method and chemical vapor deposition method.

Claims

1. A compound represented by the following Chemical Formula 1: [Chemical Formula 1] In the 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; R5to R 10 each independently hydrogen, or a linear or branched hydrocarbon group having 1 to 4 carbon atoms. 2.The compound according to claim 1, R1 to R4 are each independently any one selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, and t-butyl.

3. The compound of claim 1, R5to R 10 each independently is any one selected from the group consisting of methyl, ethyl, n-propyl, and isopropyl. 4.The compound according to claim 1, represented by the following Chemical Formulae 1-1, 1-2, or 1-3: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] In the Chemical Formulae 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 according to any one of claims 1 to 4. 6.A method for manufacturing a thin film, comprising the step of introducing the precursor composition for vapor deposition according to claim 5 into a chamber. 7.The method for manufacturing a thin film according to claim 6, comprising an atomic layer deposition (ALD) or a chemical vapor deposition (CVD). 8.The method for manufacturing a thin film according to claim 6, further comprising the step of injecting as a reaction gas any one or more selected from the group consisting of hydrogen (H2), a compound containing an oxygen (O) atom, a compound containing a nitrogen (N) atom, and a compound containing a silicon (Si) atom. 9.The method for manufacturing a thin film according to claim 8, wherein the reaction gas is any one or more selected from the group consisting of hydrogen (H2), water vapor (H2O), oxygen (O2), ozone (O3), nitrogen (N2), ammonia (NH3), hydrazine (N2H4), and silane.

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