Group 4 metal element-containing compound, precursor composition containing the same, and method for producing thin film using the same

Abstract

The present invention relates to novel Group 4 metal element-containing compounds with excellent thermal stability, precursor compositions containing the compounds, and methods for producing thin films using the precursor compositions. The novel Group 4 metal element-containing compounds and vapor deposition precursor compositions containing the compounds according to the present invention have excellent thermal stability, enabling thin film deposition over a wide temperature range and minimizing residues due to heat loss, thereby preventing side reactions during processing. Furthermore, the vapor deposition precursor compositions according to the present invention enable uniform thin film deposition, thereby ensuring excellent thin film properties.

Description

[Technical field]

[0001] The present invention relates to a Group 4 metal element-containing compound having excellent thermal stability, a precursor composition containing said compound, and a method for producing a thin film using said precursor composition. [Background technology]

[0002] The gate oxide film (gate dielectric film) used in the gate structure of MOSFET (metal-oxide-semiconductor field effect transistor), the core structure of semiconductor devices, has disadvantages such as an increase in leakage current due to the thin oxide film and the formation of a gate depletion layer due to the integration of silicon oxide, which is the original material. The capacitance is proportional to the relative dielectric constant of the capacitor insulation film and the area of ​​the electrode, and inversely proportional to the thickness. Therefore, as a method of increasing the capacitance without reducing the thickness of the thin film while using a high dielectric constant material, a capacitor with a stack type structure has been developed. The technical requirement for this is to form thin films of electrode layers and dielectric layers with uniform thickness within a structure with a certain aspect ratio. To solve this requirement, Al2O3 has been adopted as a high dielectric material from the 100nm process, and atomic layer deposition (ALD) technology has been introduced as a process to ensure the step coverage of the thin film. As the technology advances to the sub-80nm scale, oxide materials with high dielectric constants are required, and oxide films containing zirconium or hafnium (ZrO2, HfO2, etc.) are being used in the industry.

[0003] The main precursors for zirconium oxide films include TEMAZ (Tetrakis Ethyl Methyl Amino Zirconium) and CpTDMAZ (Cyclopentadienyl tris-dimethylamino zirconium). TEMAZ forms zirconium oxide films with monoclinic and triclinic crystal structures, but has the limitation that it cannot ensure step coverage due to the sudden decomposition of the precursor at temperatures above 280°C. The CpTDMAZ precursor utilizes a cyclopentadienyl group to strongly bond with metal ions through π bonds, and by introducing a dimethylamino group to suppress the heat-induced β and γ hydrogen removal reaction, it is a precursor that can realize the ALD process up to 300°C. For this reason, the precursor has been changed to CpTDMAZ instead of TEMAZ from the 30 nm process. However, it has also been confirmed that CpTDMAZ has a disadvantage in that the sudden decomposition of the precursor at temperatures above 310°C is also a disadvantage.

[0004] Meanwhile, Korean Patent Publication Nos. 10-2012-0105070 and 10-2014-0078534 disclose compounds containing Group 4 metal elements such as zirconium and Group 4 metal element-containing thin films, but there are limitations to ensuring thermal stability and improving thin film deposition uniformity due to the compound structure. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Republic of Korea Patent Publication No. 10-2012-0105070 [Patent Document 2] Republic of Korea Patent Publication No. 10-2014-0078534 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention provides a novel Group 4 metal element-containing compound applicable to atomic layer deposition (ALD) or chemical vapor deposition (CVD), and a vapor deposition precursor composition containing the same.

[0007] In particular, the present invention aims to provide a vapor deposition precursor composition that has excellent thermal stability, allows thin film deposition over a wide temperature range, produces little residue due to heat loss, prevents side reactions during processing, and allows for uniform deposition of thin films with excellent physical properties.

[0008] However, the problems to be solved by the present application are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description. [Means for solving the problem]

[0009] One aspect of the present application provides a compound represented by the following formula 1:

[0010] [ka]

[0011] In the above formula 1, M is any one selected from Group 4 metal elements, R1 to R4 each independently represent a hydrogen atom; a substituted or unsubstituted linear or branched, saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms; R5 and R6 are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, a dialkylamine group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0012] Another aspect of the present application provides a vapor deposition precursor composition comprising the compound.

[0013] Yet another aspect of the present application provides a method for producing a thin film, comprising forming a Group 4 metal element-containing thin film using the vapor deposition precursor composition. Effect of the Invention

[0014] The novel Group 4 metal element-containing compound and vapor deposition precursor composition containing the compound according to the present invention have excellent thermal stability, can be used for thin film deposition in a wide temperature range, and can prevent side reactions during processing by reducing residues caused by heat loss.

[0015] In addition, the vapor deposition precursor composition according to the present invention allows for uniform thin film deposition, thereby ensuring excellent thin film properties.

[0016] The above physical properties provide a precursor suitable for atomic layer deposition, and the deposited thin film can be used as a gate dielectric material. [Brief description of the drawings]

[0017] [Figure 1] 1 is a thermogravimetric analysis (TGA) graph comparing the thermal decomposition characteristics of a zirconium precursor (ZEA) according to Example 1 of the present application and a zirconium precursor (ZAC) according to Comparative Example 1. [Diagram 2] 1 is a thermogravimetric analysis (TGA) graph comparing the thermal decomposition characteristics of hafnium precursors (HEA, HEAM, and HGEA) according to Examples 2, 3, and 5 of the present application and a hafnium precursor (HAC) according to Comparative Example 2. [Diagram 3] 1 is a thermogravimetric analysis (TGA) graph of titanium precursor (TEAM) according to Example 4 of the present application. [Figure 4] 2 is a graph showing the deposition rate of a zirconium oxide film according to a precursor injection time in Preparation Example 1 of the present application. [Diagram 5] 4 is a graph showing the deposition rate of a zirconium oxide film according to an oxidizing agent injection time in Preparation Example 2 of the present application. [Figure 6]4 is a graph showing a deposition rate of a zirconium oxide film depending on a process temperature in Preparation Example 3 of the present application. [Figure 7] 4 is a graph showing a deposition rate of a hafnium oxide film according to a precursor injection time and a process temperature in Preparation Example 4 of the present application. [Figure 8] 4 is a graph showing the deposition rate of a hafnium oxide film according to an oxidizing agent injection time in Production Example 5 of the present application. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The present invention will be described in detail below with reference to the embodiments and examples thereof so that those skilled in the art can easily carry out the present invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments and examples described herein.

[0019] Throughout this specification, when an element is said to be "on" another element, this includes not only when the element is in contact with the other element, but also when there is another element between the two elements.

[0020] Throughout this specification, when a part is described as "comprising" a certain element, this means that it can further include other elements, but not to the exclusion of other elements, unless specifically stated to the contrary.

[0021] Additionally, throughout this specification, the words "a step of" or "a step of" do not mean "a step for".

[0022] Throughout this specification, the term "alkyl" includes linear or branched alkyl groups having 1 to 6 carbon atoms, preferably linear or branched alkyl groups having 1 to 4 carbon atoms, and all possible isomers thereof. For example, the alkyl groups include methyl (Me), ethyl (Et), n-propyl (N-propyl) and aryl groups. n Pr), iso-propyl group ( i Pr), n-butyl group ( nBu), tert-butyl group ( t Bu), iso-butyl group ( i Bu), sec-butyl group ( sec Bu), n-pentyl group, iso-pentyl group, neo-pentyl group, sec-pentyl group, tert-pentyl group, hexyl group, isohexyl group, and isomers thereof.

[0023] Throughout this specification, the term "Group 4 metal elements" refers to chemical elements belonging to Group 4 of the periodic table and can include Zr, Hf, or Ti.

[0024] Throughout this specification, the term "Cp" is represented as -C5H4 and is an abbreviation for "cyclopentadienyl group."

[0025] Hereinafter, the present application will be described in detail with reference to the accompanying drawings, but the present application is not limited to the embodiments and examples.

[0026] The present invention relates to a novel Group 4 metal element-containing compound that can be used in atomic layer deposition or chemical vapor deposition and has excellent reactivity, volatility, and thermal stability, a vapor deposition precursor composition containing the Group 4 metal element-containing compound, a method for producing a thin film using the precursor composition, and a Group 4 metal element-containing thin film produced from the precursor composition.

[0027] One aspect of the present application provides a compound represented by the following formula 1:

[0028] [ka]

[0029] In the above Chemical Formula 1, M is any one selected from Group 4 metal elements, and is preferably zirconium (Zr), hafnium (Hf) or titanium (Ti), R1 to R4 are each independently hydrogen, or a substituted or unsubstituted linear or branched, saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms; R5 and R6 are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, a dialkylamine group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0030] Preferably, R1 and R2 are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, R3 and R4 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and R5 and R6 are each independently a linear alkyl group having 1 to 4 carbon atoms or a linear dialkylamine group having 1 to 4 carbon atoms.

[0031] In one embodiment of the present application, the compound represented by Chemical Formula 1 is preferably represented by any one of Chemical Formulas 1-1 to 1-9 below.

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] [ka]

[0039] [ka]

[0040] [ka]

[0041] In the above chemical formulas 1-1 to 1-6, Me is a methyl group.

[0042] The compound according to the present invention is an amino chelate compound having a Group 4 metal element as the central metal, and has the advantages of being excellent in reactivity and volatility and being capable of being purified at a relatively low temperature.

[0043] In one embodiment of the present application, the compound represented by Formula 1 may be liquid at room temperature. In atomic layer deposition (ALD), reactants must be highly volatile, stable, and highly reactive. In ALD, reactants are separately supplied and deposited in cycles, and a monolayer or less thin film is grown by a surface reaction, and the ligand of the reactant adsorbed on the substrate is removed by a chemical reaction with another reactant that is subsequently supplied. When reactant precursor compounds are heated for atomic layer deposition, the liquid state may be much more advantageous in terms of reaction rate and process than the solid state.

[0044] Another aspect of the present application provides a vapor deposition precursor composition comprising the compound.

[0045] The vapor deposition precursor composition according to the present invention can be applied to all of the contents described above regarding the Group 4 metal element-containing compound according to the present invention, and although detailed descriptions of overlapping parts are omitted, the same can be applied even if the descriptions are omitted.

[0046] In one embodiment of the present application, the vapor deposition may include atomic layer deposition (ALD) or chemical vapor deposition (CVD), and the chemical vapor deposition may include metal organic chemical vapor deposition (MOCVD).

[0047] Yet another aspect of the present application provides a method for producing a thin film, the method comprising the step of forming a Group 4 metal element-containing thin film using the vapor deposition precursor composition, and a Group 4 metal element-containing thin film produced by the method.

[0048] The method for producing a thin film according to the present invention can be applied to all of the contents described for the Group 4 metal element-containing compound and the precursor composition containing the same according to the present invention, and although detailed descriptions of overlapping parts are omitted, the method can be equally applied even if the descriptions are omitted.

[0049] In one embodiment of the present application, forming the Group 4 metal element-containing thin film on a substrate can include introducing the vapor deposition precursor composition into a chamber, and introducing the vapor deposition precursor into a chamber can include physisorption, chemisorption, or physisorption and chemisorption.

[0050] In one embodiment of the present application, the method for producing the thin film may include both an atomic layer deposition (ALD) method in which the vapor deposition precursor composition of the present invention and a reactive gas are sequentially introduced, and a chemical vapor deposition (CVD) method in which a film is formed by continuously injecting the vapor deposition precursor of the present invention and a reactive gas.

[0051] More specifically, the deposition method may include, but is not limited to, 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.

[0052] A method for preparing a Group 4 metal element-containing thin film according to an embodiment of the present application may include, but is not limited to, providing one or more surfaces of a substrate in a reaction chamber; introducing a precursor composition including the Group 4 metal element-containing compound into the reaction chamber; and introducing a reaction gas into the reaction chamber, where a Group 4 metal element-containing thin film may be formed on the one or more surfaces of the substrate by vapor phase deposition.

[0053] The Group 4 metal element-containing thin film may include a Group 4 metal element-containing oxide film, nitride film, oxynitride film, carbide film, or carbonitride film, and specifically may be an oxide film, nitride film, oxynitride film, carbide film, or carbonitride film of zirconium, hafnium, or titanium.

[0054] In one embodiment of the present application, the reaction gas may include an oxygen-containing source, a nitrogen-containing source, a carbon-source, a silicon-source, a reducing agent, and combinations thereof.

[0055] More specifically, any one or more selected from hydrogen (H2), water (H2O), oxygen (O2), ozone (O3), ammonia (NH3), hydrazine (N2H4) and silane can be used as the reactive gas, but is not limited thereto.

[0056] Specifically, water (H2O), oxygen (O2) and ozone (O3) can be used as reactive gases to deposit Group 4 metal element-containing oxide thin films, and ammonia (NH3) or hydrazine (N2H4) can be used as reactive gases to deposit Group 4 metal element-containing nitride thin films.

[0057] In addition, hydrogen (H2) can be used as a reactive gas to deposit Group 4 metal element-containing thin films, and silane compounds can be used as a reactive gas to deposit Group 4 metal element-containing silicide thin films.

[0058] In addition, in order to assist the transfer of the precursor onto the substrate, to ensure that the inside of the reactor has an appropriate pressure for deposition, and to release impurities present in the reactor to the outside, a process of purging the reactor with an inert gas such as argon (Ar), nitrogen (N2), or helium (He) is additionally performed before and after the supply of the reaction gas. EXAMPLES

[0059] The present invention will be described in more detail with reference to the following examples. However, the following examples are provided to further explain the present invention, and the scope of the present invention is not limited to the following examples.

[0060] Synthesis example 1:N 1 ,N 2 Synthesis of -di-tert-butylpropane-1,2-diamine

[0061] Tert-butylamine ( t211.2 mL (21.04 mol) of BuNH2 was dissolved in 4 L of methylene chloride (MC). A solution of 1,000 g (4.67 mol) of 2-bromoisobutyryl bromide dissolved in 1 L of MC was slowly added to the solution at low temperature, and the solution was stirred at room temperature for 2 hours. 374.08 g (9.35 mol) of sodium hydroxide (NaOH) was added to the solution, and the reaction was refluxed for 20 hours using a reflux condenser. After the reaction was completed, water was added to the solution and extracted with MC, and the solvent and the remaining t BuNH2 was removed to obtain 709 g (yield: 76.0%) of white solid N-(tert-butyl)-2-(tert-butylamino)propanamide.

[0062] Lithium aluminum hydride (LiAlH4) 672.03g (17.7mol) was suspended in 4L of tetrahydrofurane (THF) at low temperature, and a solution of the synthesized solid in 1L of THF was slowly added at low temperature. The suspension was then refluxed for 1 day using a reflux condenser. After the reaction was completed, water was added at low temperature and extracted with MC, and the solvent was removed under reduced pressure to obtain a transparent orange liquid. The transparent orange liquid was purified under reduced pressure to obtain N, a colorless liquid represented by the following chemical formula 2. 1 ,N 2 -Di-tert-butylpropane-1,2-diamine (N 1 ,N 2 The obtained compound was 590.0 g (yield: 89%) of 1,2-di-tert-butylpropane-1,2-diamine.

[0063] [ka]

[0064] Boiling point (bp): 42℃ @ 0.2torr (bath standard) 1H-NMR(C6D6): δ1.046 ((C H 3) 3CNHCH(C H 3)CH2NHC(C H 3)3, m, 21H), δ2.277 ((CH3)3CNHCH(CH3)C H 2NHC(CH3)3, m, 1H), δ2.414 ((CH3)3CNHC H (CH3)2CH2NHC(CH3)3, m, 1H), δ2.653 ((CH3)3CNHCH(CH3)2C H 2NHC(CH3)3, m, 1H).

[0065] Synthesis example 2:N 1 ,N 2 Synthesis of -di-tert-butyl-2-methylpropane-1,2-diamine

[0066] Tert-butylamine ( t 1,431 g (19.57 mol) of 2-Bromopropanoyl bromide was dissolved in 4 L of methylene chloride (MC). A solution of 1,000 g (4.34 mol) of 2-Bromopropanoyl bromide dissolved in 1 L of MC was slowly added to the solution at low temperature and stirred at room temperature for 2 hours. 374.08 g (9.35 mol) of sodium hydroxide (NaOH) was added to the solution and the reaction was refluxed for 20 hours using a reflux condenser. After the reaction was completed, water was added to the solution and extracted with MC, and the solvent and the remaining t BuNH2 was removed to obtain 741 g (yield: 79.4%) of white solid N-(tert-butyl)-2-(tert-butylamino)-2-methylpropanamide.

[0067] Lithium aluminum hydride (LiAlH4) 655.07g (17.3mol) was suspended in 4L of tetrahydrofuran (THF) at low temperature, and a solution of the synthesized solid in 1L of THF was slowly added at low temperature. The suspension was then refluxed for 1 day using a reflux condenser. After the reaction was completed, water was added at low temperature and extracted with MC, and the solvent was removed under reduced pressure to obtain a transparent orange liquid. The transparent orange liquid was purified under reduced pressure to obtain N, a colorless liquid represented by the following chemical formula 3. 1 ,N 2 -Di-tert-methylbutylpropane-1,2-diamine (N 1 ,N 2 The obtained compound was 604.0 g (yield: 85%) of 1,2-di-tert-butyl-2-methylpropane-1,2-diamine.

[0068] [ka]

[0069] Boiling point: 40℃ @ 0.2torr (bath standard) 1 H-NMR(C6D6): δ1.049 ([(C H 3)3CNHC(CH3)2CH2NHC(CH3)3], s, 9H) δ1.179 ([(CH3)3CNHC(C H 3) 2CH2NHC(CH3)3], s, 6H), δ1.183 ([(CH3)3CNHC(CH3)2CH2NHC(C H 3)3], s, 9H), δ2.341 ([(CH3)3CNHC(CH3)2C H 2NHC(CH3)3], s, 2H).

[0070] Example 1: 1 ,N 2 Synthesis of -di-tert-butylpropane-1,2-diamine-Zr-(NMe2)2 (ZEA)

[0071] In flask 1, 3.74 g (0.016 mol) of zirconium chloride (ZrCl4) and 20 mL of hexane were placed, and a solution of 4.3 g (0.016 mol) of tetrakis(dimethylamino)zirconium (TDMA-Zr) dissolved in 10 mL of hexane was added at low temperature, and then the mixture was stirred at room temperature for 18 hours.

[0072] In flask 2, the N 1 ,N 2 -Di-tert-butylpropane-1,2-diamine [N 1 ,N 2 -di-tert-butylpropane-1,2-diamine]6g (0.032mol) was dissolved in 20mL of hexane, and n-butyllithium ( n BuLi) 25 mL (0.064 mol) was slowly added at low temperature, and the mixture was stirred at room temperature for 18 hours.

[0073] The solution in flask 2 was slowly added to flask 1 at low temperature and then stirred at room temperature for 18 hours. The reactants were filtered and the solvent was removed under reduced pressure to obtain a transparent orange liquid. The resulting liquid was purified under reduced pressure to obtain a pale yellow liquid, (N 1 ,N 2 -Di-tert-butylpropane-1,2-diamino)-bis(dimethylamino)zirconium [(N 1 ,N 2 The obtained compound was synthesized by the method of the present invention and synthesized by the method of the present invention. The ...

[0074] [ka]

[0075] Molecular Weight: 363.70 Boiling point (bp): 100℃ @ 0.2torr (bath standard) 1 H-NMR(C6D6): δ1.159 ([(C H3) 3CNCH(CH3)CH2NC(C H 3) 3]-Zr-[N(CH3)2]2, d, 18H), δ1.564 ([(CH3)3CNCH(C H 3)CH2NC(CH3)3]-Zr-[N(CH3)2]2, d, 3H), δ2.858 ([(CH3)3CNCH(CH3)C H 2NC(CH3)3]-Zr-[N(CH3)2]2, d, 1H), δ3.066 ([(CH3)3CNCH(CH3)CH2NC(CH3)3]-Zr-[N(C H 3)2]2, d, 12H), δ3.309 ([(CH3)3CNC H (CH3)CH2NC(CH3)3]-Zr-[N(CH3)2]2, m, 1H), δ3.988 ([(CH3)3CNCH(CH3)C H 2NC(CH3)3]-Zr-[N(CH3)2]2, dd, 1H).

[0076] Example 2: 1 ,N 2 Synthesis of -di-tert-butylpropane-1,2-diamine-Hf-(NMe2)2 (HEA)

[0077] In flask 1, 44.9 g (0.14 mol) of hafnium chloride (HfCl4) and 300 mL of hexane were added, and a solution of 50 g (0.14 mol) of tetrakis(dimethylamino)hafnium (TDMAHf) dissolved in 100 mL of hexane was added at low temperature, and then the mixture was stirred at room temperature for 18 hours.

[0078] In flask 2, the N 1 ,N 2 -Di-tert-butylpropane-1,2-diamine (N 1 ,N 2 -di-tert-butylpropane-1,2-diamine) 52g (0.28mol) was dissolved in 50ml of hexane, and n-butyllithium (n BuLi)225mL (0.56mol) was slowly added at low temperature, and the mixture was stirred at room temperature for 18 hours.

[0079] The solution in flask 2 was slowly added to flask 1 at low temperature and then stirred at room temperature for 18 hours. The reactants were filtered and the solvent was removed under reduced pressure to obtain a transparent orange liquid. The resulting liquid was purified under reduced pressure to obtain a pale yellow liquid, (N 1 ,N 2 -Di-tert-butylpropane-1,2-diamino)-bis(dimethylamino)hafnium[(N 1 ,N 2 The obtained compound was 78 g (yield: 61%) of [-di-tert-butylpropane-1,2-diamino)-bis(dimethylamino)Hf].

[0080] [ka]

[0081] Molecular Weight: 450.96 Boiling point: 98℃ @ 0.2torr (bath standard) 1 H-NMR(C6D6): δ1.141 ([(C H 3) 3CNCH(CH3)CH2NC(C H 3) 3]-Hf-[N(CH3)2]2, d, 18H), δ1.537 ([(CH3)3CNCH(C H 3)CH2NC(CH3)3]-Hf-[N(CH3)2]2, d, 3H), δ2.914 ([(CH3)3CNCH(CH3)C H 2NC(CH3)3]-Hf-[N(CH3)2]2, d, 1H), δ3.079 ([(CH3)3CNCH(CH3)CH2NC(CH3)3]-Hf-[N(C H 3)2]2, d, 12H), δ3.423 ([(CH3)3CNC H(CH3)CH2NC(CH3)3]-Hf-[N(CH3)2]2, m, 1H), δ3.941 ([(CH3)3CNCH(CH3)C H 2NC(CH3)3]-Hf-[N(CH3)2]2, dd, 1H).

[0082] Example 3: N 1 ,N 2 Synthesis of -di-tert-butylpropane-1,2-diamine-Hf-Me2 (HEAM)

[0083] In flask 1, the N 1 ,N 2 -Di-tert-butylpropane-1,2-diamine-Hf-(NMe2)220g (0.063mol) and toluene100mL were added, trimethylsilyl chloride (TMS-Cl)14.95g (0.138mol) was added at low temperature, and the mixture was stirred at room temperature for 18 hours. The reaction mixture was filtered to obtain the intermediate HEA-Cl2.

[0084] In flask 2, 14.3 g (0.033 mol) of the reactant HEA-Cl2 and 100 mL of toluene were placed, and 36 mL of methyllithium solution was added at low temperature, followed by stirring at room temperature for 18 hours. The reactant was filtered, and the solvent was removed under reduced pressure to obtain a transparent orange liquid. The resulting liquid was purified under reduced pressure to obtain a pale yellow liquid, (N 1 ,N 2 -Di-tert-butylpropane-1,2-diamine)-bis(methyl)hafnium[N 1 ,N 2 -di-tert-butylpropane-1,2-diamine-Hf-Me2] 11 g (yield: 58%) was obtained.

[0085] [ka]

[0086] Molecular Weight: 392.88 Boiling point: 80℃ @ 0.4torr (bath standard) 1 H-NMR(C6D6): δ0.130 ([(CH3)3CNCH(CH3)CH2NC(CH3)3]-Hf-(C H 3)2, s, 6H), δ1.185 ([(C H 3) 3CNCH(CH3)CH2NC(C H 3) 3]-Hf-(CH3)2, d, 18H), δ1.390 ([(CH3)3CNCH(C H 3)CH2NC(CH3)3]-Hf-(CH3)2, d, 3H), δ2.805 ([(CH3)3CNCH(CH3)C H 2NC(CH3)3]-Hf-(CH3)2, d, 12H), δ3.480 ([(CH3)3CNC H (CH3)CH2NC(CH3)3]-Hf-(CH3)2, m, 1H), δ3.905 ([(CH3)3CNCH(CH3)C H 2NC(CH3)3]-Hf-(CH3)2, dd, 1H).

[0087] Example 4: N 1 ,N 2 Synthesis of -di-tert-butylpropane-1,2-diamine-Ti-Me2 (TEAM)

[0088] In flask 1, 25.0 g (0.13 mol) of titanium chloride (TiCl4) and 200 mL of toluene were stirred at low temperature.

[0089] In flask 2, the N 1 ,N 2 -Di-tert-butylpropane-1,2-diamine (N 1 ,N 224.6g (0.13mol) of TEA-di-tert-butylpropane-1,2-diamine was dissolved in 50mL of toluene, and 40.4mL (0.29mol) of triethylamine was slowly added at low temperature, and the mixture was stirred at room temperature for 18 hours. The reaction mixture was filtered to obtain the intermediate TEA-Cl2.

[0090] In flask 3, 10.0 g (0.033 mol) of the reactant TEA-Cl2 and 100 mL of toluene were placed, and 45.4 mL of methyllithium solution was added at low temperature, followed by stirring at room temperature for 18 hours. The reactant was filtered, and the solvent was removed under reduced pressure to obtain a transparent orange liquid. The resulting liquid was purified under reduced pressure to obtain a transparent liquid, (N 1 ,N 2 -Di-tert-butylpropane-1,2-diamino)-bis(methyl)titanium[(N 1 ,N 2 The obtained compound was 7.1 g (yield: 60%) of [-di-tert-butylpropane-1,2-diamino)-bis(methyl)Ti].

[0091] [ka]

[0092] Molecular Weight: 262.26 Boiling point: 90℃ @ 0.4torr (bath standard) 1 H-NMR(C6D6): δ0.580 ([(CH3)3CNCH(CH3)CH2NC(CH3)3]-Ti-(C H 3)2, s, 3H), δ0.620 ([(CH3)3CNCH(CH3)CH2NC(CH3)3]-Ti-(C H 3)2, s, 3H), δ1.310 ([(CH3)3CNCH(C H 3)CH2NC(CH3)3]-Ti-(CH3)2, d, 3H), δ1.355 ([(CH 3) 3CNCH(CH3)CH2NC(C H 3) 3]-Ti-(CH3)2, d, 18H), δ2.675 ([(CH3)3CNCH(CH3)C H 2NC(CH3)3]-Ti-(CH3)2, d, 1H), δ3.350 ([(CH3)3CNC H (CH3)CH2NC(CH3)3]-Ti-(CH3)2, m, 1H), δ3.930 ([(CH3)3CNCH(CH3)C H 2NC(CH3)3]-Ti-(CH3)2, dd, 1H).

[0093] Example 5: N 1 ,N 2 Synthesis of -di-tert-butyl-2-methylpropane-1,2-diamine-Hf-(NMe2)2 (HGEA)

[0094] In flask 1, 44.9 g (0.14 mol) of hafnium chloride (HfCl4) and 300 mL of hexane were placed, and a solution of 50 g (0.14 mol) of tetrakis(dimethylamino)hafnium (TDMA-Hf) dissolved in 100 mL of hexane was added at low temperature, and then the mixture was stirred at room temperature for 18 hours.

[0095] In flask 2, the N 1 ,N 2 -Di-tert-methylbutylpropane-1,2-diamine (N 1 ,N 2 56.1 g (0.28 mol) of n-di-tert-butyl-2-methylpropane-1,2-diamine was dissolved in 50 mL of hexane, and n-butyllithium ( n BuLi)225mL (0.56mol) was slowly added at low temperature, and the mixture was stirred at room temperature for 18 hours.

[0096] The solution in flask 2 was slowly added to flask 1 at low temperature and then stirred at room temperature for 18 hours. The reactants were filtered and the solvent was removed under reduced pressure to obtain a transparent orange liquid. The resulting liquid was purified under reduced pressure to obtain a pale yellow liquid, (N 1 ,N 2 -Di-tert-butyl-2-methylpropane-1,2-diamino)-bis(dimethylamino)hafnium[(N 1 ,N 2 The obtained compound was 78 g (yield: 61%) of [-di-tert-butyl-2-methylpropane-1,2-diamino)-bis(dimethylamino)Hf].

[0097] [ka]

[0098] Molecular Weight: 464.99 Boiling point: 111℃ @ 0.4torr (bath standard) 1 H-NMR(C6D6): δ1.180 ([(C H 3)3CNC(CH3)2CH2NC(CH3)3]-Hf-[N(CH3)2]2, s, 9H), δ1.280 ([(CH3)3CNC(CH3)2CH2NC(C H 3) 3]-Hf-[N(CH3)2]2, s, 9H), δ1.400 ([(CH3)3CNC(C H 3)2CH2NC(CH3)3]-Hf-[N(CH3)2]2, s, 6H), δ3.070 ([(CH3)3CNC(CH3)2CH2NC(CH3)3]-Hf-[N(C H 3)2]2, s, 12H), δ3.110 ([(CH3)3CNC(CH3)2C H 2NC(CH3)3]-Hf-[N(CH3)2]2, s, 2H).

[0099] Example 1: Characterization of vapor-deposited zirconium precursors

[0100] In this experimental example, as shown in FIGS. 1 to 3, in order to analyze the properties of the vapor deposition precursors prepared in Examples 1 to 5, thermogravimetric analysis (TGA) and the temperature at which the weight is reduced by half [T 1 / 2 The results are summarized in Table 1 below.

[0101] Specifically, when analyzing the characteristics of the vapor deposition precursor prepared in Example 1 (ZEA), Comparative Example 1 [CpTDMAZ (Cyclopentadienyl Tris(dimethylamino) Zirconium; ZAC)] was set as a control, and when analyzing the characteristics of the vapor deposition precursor prepared in Example 2 (HEA), Example 3 (HEAM), and Example 5 (HGEA), Comparative Example 2 [CpTDMAH (Cyclopentadienyl Tris(dimethylamino) Hafnium; HAC)] was set as a control.

[0102] [Table 1]

[0103] Amino chelate compounds are compounds that are often used as precursors and have excellent reactivity and volatility. For this reason, in this example, an alkyl chain having dimethyl was used to synthesize a precursor with a chelate structure on the central metal (zirconium or hafnium). Among existing precursors, it is characterized by being refined at a similar temperature to CpTDMAZ and CpTDMAH used as comparative examples, and is expected to have excellent volatility. In this example, a precursor was obtained using a diamine-based organic ligand, and the central metal was deformed to compare and analyze the changes in physical properties. Therefore, N 1 ,N 2 -di-tert-butylpropane-1,2-diamine Zr(NMe2)2 and N 1 ,N 2-di-tert-butylpropane-1,2-diamine Hf(NMe2)2 was synthesized and their physical properties were confirmed. The new zirconium and hafnium compounds synthesized in this example were able to be purified at relatively low temperatures as liquid compounds.

[0104] Manufacturing Example 1: Manufacturing of zirconium oxide film using atomic layer deposition (ALD) 1

[0105] A zirconium oxide film was produced by atomic layer deposition (ALD) using the zirconium compound synthesized in Example 2 as a precursor. The temperature of the precursor used in this production example was maintained at 90°C. A boron-doped P-type silicon wafer was used as the substrate. Ozone was used as the oxidizing agent, and the ozone concentration was 144 g / m 3 was generated with 125 sccm oxygen gas. The inert gas argon was used for purging and precursor carrier purposes. The flow rate of the purging argon was 500 sccm, and the flow rate of the carrier argon was 10 sccm.

[0106] The following steps were performed in sequence: (injection of precursor for X seconds)-(injection of precursor purging argon for 10 seconds)-(injection of oxidizing agent for 3 seconds)-(injection of oxidizing agent purging argon for 10 seconds), which constituted one cycle. In the supply of the precursor, the X seconds was 1 to 7 seconds, the process temperature was 260°C, and the zirconium oxide film was deposited in 200 cycles.

[0107] As shown in FIG. 4, increasing the precursor injection from 1 to 7 seconds increased the deposition rate from 0.92 Å / cycle to 1.17 Å / cycle.

[0108] Production Example 2: Production of zirconium oxide film using atomic layer deposition (ALD) 2

[0109] The injection time of the precursor purge argon, the injection time of the oxidant purge argon, the process temperature, and the number of cycles were maintained the same as in Preparation Example 1, but the injection time of the precursor was fixed at 5 seconds and the injection time of the oxidant was set to 1 to 5 seconds to deposit the zirconium oxide film.

[0110] As can be seen from Figure 5, the deposition rate remained constant at 1.11 Å / cycle even though the injection time of the oxidant was increased from 1 s to 5 s, which means that a self-limited reaction of the oxidant occurred at an injection time of 1 s.

[0111] Manufacturing Example 3: Manufacturing of zirconium oxide film using atomic layer deposition (ALD) 3

[0112] The injection time of the precursor purge argon, the injection time of the oxidant purge argon, and the number of cycles were kept the same as in Preparation Example 1 and Preparation Example 2, the injection time of the precursor and the injection time of the oxidant were fixed at 5 seconds and 3 seconds, respectively, and the process temperature was set to 220°C to 320°C to deposit the zirconium oxide film.

[0113] As shown in FIG. 6, when the process temperature was 220°C to 280°C, the deposition rate was maintained at 1.10 Å / cycle to 1.25 Å / cycle, whereas at 300°C, the deposition rate was 1.33 Å / cycle. When the process temperature was increased to 320°C, the deposition rate further increased to 1.67 Å / cycle.

[0114] In atomic layer deposition (ALD), the range in which the deposition rate is constant regardless of the process temperature is called the ALD window, and the above results indicate that the precursor synthesized in Example 1 exhibits an ALD window of 220°C to 280°C. On the other hand, above 300°C, the deposition rate increases in proportion to the process temperature, which is a similar region to CVD.

[0115] Manufacturing Example 4: Manufacturing of hafnium oxide film using atomic layer deposition (ALD) 1

[0116] A hafnium oxide film was produced by atomic layer deposition (ALD) using the hafnium compound synthesized in Example 2 as a precursor. The temperature of the precursor used in this production example was maintained at 80° C. The type of substrate, the type of oxidizer, the concentration of ozone, and the flow rate of purge and carrier argon were the same as in Production Example 1.

[0117] (Injection of precursor for X seconds)-(Injection of precursor purge argon for 40 seconds)-(Injection of oxidant for 5 seconds)-(Injection of oxidant purge argon for 10 seconds) were carried out in sequence, which was defined as one cycle. In the supply of precursor, X was set to 5 to 15 seconds, the process temperature was set to 240°C to 260°C, and a hafnium oxide film was deposited in 200 cycles.

[0118] As shown in Figure 7, the deposition rate increased from 0.88 Å / cycle to 1.03 Å / cycle by increasing the precursor injection time from 5 s to 15 s at a process temperature of 240°C, and increased from 0.87 Å / cycle to 1.08 Å / cycle and from 0.89 Å / cycle to 1.10 Å / cycle at process temperatures of 250°C and 260°C, respectively.

[0119] Production Example 5: Production of hafnium oxide film using atomic layer deposition (ALD) 2

[0120] The precursor purge argon injection time, oxidant purge argon injection time, and cycle number were maintained the same as in Preparation Example 4, the precursor injection time was 15 seconds, the process temperature was fixed at 250°C, and the oxidant injection time was 1 to 5 seconds to deposit a hafnium oxide film.

[0121] As can be seen from Figure 8, even though the injection time of the oxidant was increased from 1 second to 5 seconds, the deposition rate remained constant at 1.07 Å / cycle. This means that a self-limited reaction of the oxidant occurs at an injection time of 1 second, as mentioned in Preparation Example 2. [Industrial Applicability]

[0122] The novel Group 4 metal element-containing compound and vapor deposition precursor composition containing the compound according to the present invention have excellent thermal stability, can be used for thin film deposition in a wide temperature range, and can prevent side reactions during processing by reducing residues caused by heat loss.

[0123] In addition, the vapor deposition precursor composition according to the present invention allows for uniform thin film deposition, thereby ensuring excellent thin film properties.

[0124] The above physical properties provide a precursor suitable for atomic layer deposition, and the deposited thin film can be used as a gate dielectric material.

Claims

1. A compound represented by the following chemical formula 1: 【Chemistry 1】 In the above Chemical Formula 1, M is any one selected from the group 4 metal elements, R 1 and R 2 are tert-butyl groups; R 3 and R 4 are each independently a hydrogen atom or a methyl group; R 5 and R 6 are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, a dialkylamine group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; R 3 and R 4 At least one of these is a methyl group.

2. The compound according to claim 1 , wherein M is zirconium (Zr), hafnium (Hf) or titanium (Ti).

3. The compound represented by the formula 1 is the compound according to claim 1, which is represented by any one of the following formulas 1-1 to 1-9: 【Chemistry 1-1】 【Chemistry 1-2】 【Chemistry 1-3】 【Chemistry 1-4】 【Chemistry 1-5】 【Chemistry 1-6】 【Chemistry 1-7】 【Chemistry 1-8】 【Chemistry 1-9】 In the above chemical formulas 1-1 to 1-6, Me is a methyl group.

4. A vapor deposition precursor composition comprising a compound according to any one of claims 1 to 3.

5. A method for producing a thin film comprising forming a Group 4 metal element-containing thin film using the vapor deposition precursor composition of claim 4.

6. 6. The method of claim 5, wherein forming the Group 4 metal element-containing thin film on a substrate comprises introducing the vapor deposition precursor composition into a chamber.

7. The method of claim 5, wherein the method comprises Atomic Layer Deposition (ALD) or Chemical Vapor Deposition (CVD).

8. 6. The method for producing a thin film according to claim 5, wherein the Group 4 metal element-containing thin film is a zirconium-containing thin film, a hafnium-containing thin film, or a titanium-containing thin film.

9. The method for producing a thin film according to claim 5, further comprising the step of injecting any one or more selected from an oxygen-containing source, a nitrogen-containing source, a carbon source, a silicon source, and a reducing agent as a reactive gas.

10. The reaction gas is hydrogen (H 2 ), water (H 2 O), oxygen (O 2 ), ozone (O 3 ), ammonia (NH 3 ), hydrazine (N 2 H 4 10. The method for producing a thin film according to claim 9, wherein the compound is at least one selected from the group consisting of silane and silane.

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