Silicon precursor compound, silicon-containing film-forming composition containing the same, and method for forming a film using the silicon-containing film-forming composition.

Abstract

The present invention relates to a silicon precursor compound, a preparation method for the silicon precursor compound, a silicon-containing film-forming composition comprising the silicon precursor compound, and a method for forming a silicon-containing film by using the silicon-containing film-forming composition.The silicon-containing film-forming composition comprises a silicon precursor compound having a specific structure, so that the thickness of the silicon-containing film can be controlled to be very thin by atomic layer deposition (ALD), and when the silicon-containing composite film is formed by combining the ALD cycle of forming the silicon-containing film with the ALD cycle of forming the film containing another metal, the silicon content of the silicon-containing composite film can be precisely controlled within a small range.

Description

[Technical Field]

[0001] The present invention relates to a silicon precursor compound, a composition for forming a silicon-containing film comprising the silicon precursor compound, and a method for forming a film using the composition for forming a silicon-containing film. [Background technology]

[0002] In recent years, there has been active research into the application of dielectric films to semiconductor devices, specifically by doping high-k dielectric materials such as zirconium oxide (ZrO2) with a small amount of silicon (Si) to reduce leakage current. However, excessive silicon content in a dielectric film reduces its dielectric constant, so it is necessary to adjust the silicon content of silicon-containing films to a low level.

[0003] In this regard, a method for forming a silicon-containing film with a silicon content of 1 to 4 atomic percent has been disclosed, for the purpose of application to dielectric films of DRAM, by combining an atomic layer deposition (ALD) cycle for forming a zirconium oxide film (ZrO2) and an ALD cycle for forming a silicon oxide film (SiO2) (Patent Document 1).

[0004] Furthermore, a semiconductor device using a dielectric film stack in which leakage current is reduced by applying an SiO2 film having a thickness of 0.1 to 0.2 nm has been disclosed (Patent Document 2).

[0005] These patent documents disclose techniques for controlling silicon content or the thickness of SiO2 films. However, the deposition rate of gas supply in SiO2 films can only be controlled by an increase of 0.6 Å / cycle or more, and there are still limitations in more precisely controlling the thickness of SiO2 films.

[0006] On the other hand, in order to control the thickness of the SiO2 film within the range of 0.1 to 0.2 nm, it is necessary to use the composition for forming the silicon-containing film at a sufficiently low ALD gas supply rate. Furthermore, a low ALD gas supply rate is advantageous for controlling the silicon content when forming a film containing very small amounts of silicon.

[0007] Therefore, by controlling the film deposition rate of ALD gas supply, it is necessary to develop novel silicon precursor compounds and compositions for forming films that contain such silicon precursor compounds, which can uniformly and extremely thin silicon-containing films and control the silicon content of the silicon-containing films to a low level. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] U.S. Patent Application Publication No. 2010 / 0035439 [Patent Document 2] U.S. Patent Application Publication No. 2020 / 0020780 [Disclosure of the Invention] technical challenges

[0009] The technical problem to be solved by the present invention is to provide a novel silicon precursor composition that can control the thickness of a silicon-containing film to be very thin and the silicon content of the silicon-containing film to a very low level, and a composition for forming a silicon-containing film that includes such a silicon precursor composition.

[0010] Another technical problem to be solved by the present invention is to provide a method for forming a silicon-containing film, wherein a composition for forming a silicon-containing film that can achieve the above properties is used.

[0011] However, the problems to be solved by the present invention 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. Solution to the problems

[0012] To achieve the above object, the present invention provides a silicon precursor compound represented by Formula I-a.

[0013]

Chemical formula

[0014] In Formula I-a, n is 0 or 1, R 1 is hydrogen, and R 2 is independently selected from the group consisting of hydrogen, -SiH3, a linear or branched C1-C4 alkyl group, and -N(R a R b )(wherein R a and R b are each independently selected from the group consisting of linear or branched C1-C4 alkyl groups.), and R 3 to R 14 are each independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, provided that at least one of R 3 to R 5 is not hydrogen, and at least one of R 6 to R 8 is not hydrogen.

[0015] To achieve another object, the present invention provides a composition for forming a silicon-containing film, which contains a silicon precursor compound represented by Formula I.

[0016]

Chemical formula

[0017] In Formula I, n is 0 or 1, R 1 and R 2These are, independently, hydrogen, -SiH3, a linear or branched C1-C4 alkyl group, and -N(R a R b )(wherein, R a and R b Each is independently selected from the group consisting of linear or branched C1-C4 alkyl groups. ) is selected from the group consisting of R 3 ~R 14 Each is independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, provided that R 3 ~R 5 At least one of them is not hydrogen, R 6 ~R 8 At least one of them is not hydrogen.

[0018] To achieve another objective, the present invention provides a method for forming a silicon-containing film, comprising using a composition for forming a silicon-containing film comprising a silicon precursor compound represented by formula I. Advantageous effects of the invention

[0019] The silicon precursor compound according to the embodiment of the present invention, by having a specific structure, can form a silicon-containing film that is very thin, uniform in thickness, and of excellent quality.

[0020] Furthermore, the composition for forming a silicon-containing film, which includes a silicon precursor compound according to an embodiment of the present invention, allows for the control of the silicon-containing film thickness to be extremely thin and uniform by atomic layer deposition (ALD). A silicon-containing film thus formed, having a thin and uniform thickness, can be advantageously applied to dielectric film stacks and the like.

[0021] Alternatively, a silicon-containing composite film containing silicon and another metal may be formed by combining an ALD cycle (gas supply cycle) for forming a silicon-containing film using a composition for forming a silicon-containing film with an ALD cycle for forming a film containing another metal. In such a case, the silicon content of the silicon-containing composite film can be precisely controlled within a narrow range. [Brief explanation of the drawing]

[0022] [Figure 1] This graph shows the rate of film formation (GPC) of ALD gas supply relative to the film formation temperature when a silicon-containing film is formed using a composition for forming a silicon-containing film, each containing the silicon precursor compounds of Examples 1, 4, 5, 6, and 9 of the present invention, as well as Comparative Examples 1 and 2, via atomic layer deposition (ALD). [Figure 2] This graph shows the results of thermogravimetric analysis (TGA) measurements of silicon precursor compounds in Examples 1, 4, 5, 6, and 9 of the present invention. [Best Mode for Carrying Out the Invention]

[0023] The present invention is described in more detail below.

[0024] Furthermore, in this specification, when it is mentioned that an element is formed "on" another element, it means not only that one element is formed directly "on" another element, but also that other elements (multiple) are interposed between them.

[0025] In this specification, unless otherwise indicated, when a part is said to "comprising" an element, it should be understood that the part may include the other elements, rather than excluding them.

[0026] Unless otherwise indicated, all numbers and expressions relating to the quantities of components, reaction conditions, etc., used herein should be understood to be modified by the term "approximately." In this specification, unless otherwise specified, the terms “film” and “thin film” refer to both “film” and “thin film.”

[0027] In this specification, the term "alkyl" or "alkyl group" includes linear or branched alkyl groups and all possible isomers thereof. For example, alkyl or alkyl groups include methyl (Me), ethyl (Et), n-propyl ( n Pr), isopropyl group ( i Pr), n-butyl group ( n Bu), isobutyl group ( i Bu), tert-butyl group (tert-Bu, t Bu), and sec-butyl group ( sec The scope includes not only Bu) and the like, but also their isomers, etc., but alkyl or alkyl groups are not limited to these.

[0028] [Composition for forming a silicon-containing film] Embodiments of the present invention provide compositions for forming silicon-containing films, comprising a silicon precursor compound represented by formula I.

[0029] [ka]

[0030] In equation I, n is either 0 or 1, and R 1 and R 2 These are, independently, hydrogen, -SiH3, a linear or branched C1-C4 alkyl group, and -N(R a R b )(wherein, R a and R b Each is independently selected from the group consisting of linear or branched C1-C4 alkyl groups. ) is selected from the group consisting of R 3 ~R 14 Each is independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, provided that R 3 ~R 5 At least one of them is not hydrogen, R 6 ~R 8 At least one of them is not hydrogen.

[0031] The composition for forming a silicon-containing film according to embodiments of the present invention contains a silicon precursor compound represented by formula I, and therefore, the thickness of the silicon-containing film can be controlled to be very thin and uniform by atomic layer deposition (ALD).

[0032] In detail, a composition for forming a silicon-containing film, comprising a silicon precursor compound having a specific structure, allows for a low film formation rate (growth per cycle) (GPC) with ALD gas supply, and enables the formation of extremely thin silicon-containing films by ALD.

[0033] For example, when a conventional composition for forming a silicon-containing film having a GPC of approximately 0.06 nm / cycle is used, one ALD gas supply cycle forms an SiO2 film with a thickness of 0.06 nm, two ALD gas supply cycles form an SiO2 film with a thickness of 0.12 nm, and it is not possible to form an SiO2 film with a thickness of 0.1 nm by ALD. When the silicon-containing film formation composition of the present invention, which has a significantly smaller GPC than the conventional composition, is used, it is advantageous to form an SiO2 film with a thickness of 0.5 nm or less, for example, about 0.1 to 0.2 nm, by ALD. The SiO2 film thus formed, having an extremely thin thickness, can be advantageously applied to dielectric film stacks and the like (see Patent Document 2).

[0034] Furthermore, when forming a silicon-containing composite film containing silicon and another metal by combining an ALD cycle (gas supply cycle) for forming a silicon-containing film using a composition for forming a silicon-containing film with an ALD cycle for forming a film containing another metal, the silicon content of the silicon-containing composite film can be precisely controlled. For example, when adjusting the silicon content of a silicon-containing composite film to 1-4 elemental percent, the steps can be precisely controlled.

[0035] Furthermore, silicon precursor compounds are highly volatile, exist in a liquid state at room temperature, and can provide high-quality silicon-containing films in various ways, which can be advantageous in terms of product diversity, superior quality, and manufacturing processes.

[0036] According to embodiments of the present invention, the composition for forming a silicon-containing film may include a silicon precursor compound represented by the above formula I. More specifically, in formula I, R 1 and R 2 Each of these may be independently selected from the group consisting of hydrogen, -SiH3, linear or branched C1-C3 alkyl groups, and -N(CH3)2, R 3 ~R 14 Each of these may be independently selected from the group consisting of hydrogen and linear or branched C1-C3 alkyl groups.

[0037] More specifically, the composition for forming a silicon-containing film may be a composition comprising a silicon precursor compound represented by any one of formulas 5 to 16.

[0038] [ka]

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049] [ka]

[0050] The composition for forming a silicon-containing film according to embodiments of the present invention comprises a silicon precursor compound having the above structure. Therefore, when a silicon-containing film is formed by ALD, the film formation rate of the ALD gas supply can be easily controlled, the thickness of the silicon-containing film can be controlled to be uniform and very thin, and the silicon content of the silicon-containing film can be controlled to be low.

[0051] In particular, when comparing a composition for forming a silicon-containing film with a composition for forming a silicon-containing film that contains a commonly used silicon precursor compound, the film deposition rate of the SiO2 film using ALD gas can be controlled to a low level. Therefore, in high aspect ratio processes, such as processes for DRAM capacitors that require precise thickness control, there is a significant advantage in achieving silicon-containing films with extremely thin thicknesses and excellent step coverage.

[0052] More specifically, when the SiO2 film is formed by ALD using a composition for forming a silicon-containing film, a gas-supplied deposition rate (GPC) of, for example, 0.07 to 0.4 Å / cycle, for example, 0.1 to 0.35 Å / cycle, or for example, 0.1 to 0.2 Å / cycle can be achieved in a temperature range of 150°C to 450°C, more specifically 250°C to 400°C or 250°C to 350°C. In particular, when the SiO2 film is formed by ALD using a composition for forming a silicon-containing film, the gas-supplied deposition rate may be, for example, 0.1 to 0.3 Å / cycle, for example, 0.15 to 0.3 Å / cycle, for example, 0.15 to 0.25 Å / cycle, or for example, 0.15 to 0.2 Å / cycle at about 300°C.

[0053] When an SiO2 film is formed by ALD using a composition for forming a silicon-containing film, if the deposition rate of the ALD gas supply satisfies the above range of 150°C to 450°C, more specifically 250°C to 400°C or 250°C to 350°C, for example at 300°C, a thin silicon-containing film can be formed, which may be advantageous for forming an extremely thin film used as a dielectric film in a semiconductor device. For example, when an SiO2 film is formed by ALD using a composition for forming a silicon-containing film, the ALD may be advantageous for forming an SiO2 film having a thickness of about 0.5 nm or less, for example, 0.1 to 0.2 nm.

[0054] [Method for forming a silicon-containing film] According to embodiments of the present invention, a method for forming a silicon-containing film may be provided, which includes using a composition for forming a silicon-containing film comprising a silicon precursor compound represented by Formula 1.

[0055] More specifically, a method for forming a silicon-containing film may involve depositing a silicon-containing film on a substrate using a composition for forming a silicon-containing film that comprises a silicon precursor compound represented by Formula 1.

[0056] The deposition method for the silicon-containing film may be any method and / or equipment known in the art, and if necessary, one or more additional reactant gases may be used.

[0057] According to embodiments of the present invention, in a method for forming a silicon-containing film, a substrate is placed in a reaction chamber, and then a composition for forming a silicon-containing film, which includes a silicon precursor compound, is conveyed onto the substrate using a transport gas or diluent gas, and a silicon-containing film is formed at a deposition temperature of 150°C to 450°C.

[0058] In detail, methods for depositing silicon-containing films may include, for example, chemical vapor deposition (CVD) or ALD at temperatures of 250°C to 400°C, or 250°C to 350°C. This method for forming silicon-containing films can be used for other purposes, such as dielectric films in memory semiconductor devices, logic semiconductor devices, and display devices.

[0059] Furthermore, a single gas or a mixture of gases selected from the group consisting of argon (Ar), nitrogen (N2), helium (He), and hydrogen (H2) can be used as the transport gas or diluent.

[0060] When a silicon oxide film, a silicon-containing composite metal oxide film, or a silicon-containing nanomultilayer film is formed using a composition for forming a silicon-containing film that includes a silicon precursor compound, an oxygen-containing oxygen source may be used as the reaction gas.

[0061] In other words, if the silicon-containing film includes at least one selected from the group consisting of silicon-containing oxide films and silicon-containing composite metal oxide films, and the film is formed by a deposition method, an oxygen source including at least one selected from the group consisting of water vapor (H2O), oxygen (O2), oxygen plasma (O2 plasma), nitrogen oxides (NO, N2O, N2O2), nitrogen oxide plasma (N2O plasma), hydrogen peroxide (H2O2), and ozone (O3) can be used as a reaction gas.

[0062] Silicon-containing composite metal oxide films may, but are not limited to, Hf-Si-O, Zr-Si-O, Ti-Si-O, Zr-Al-Si-O, Ti-Al-Si-O, Zr-Hf-Si-O, and Zr-Hf-Al-Si-O. More specifically, silicon-containing composite metal oxide films are ternary compound films, particularly ternary oxide films, containing silicon and one type of other metal, such as Zr x Si 1-x O2 or Hf y Si 1-y It may also be O2. The silicon-containing composite metal oxide film is a quaternary compound film containing silicon and two other types of metals, in particular a quaternary oxide film, for example, Zr x Hf y Si 1-x-y O2 @.

[0063] The silicon-containing nanomultilayer film or dielectric film stack may be, for example, ZAZTS(ZrO2 / Al2O3 / ZrO2 / TiO2 / SiO2), ZAZATS(ZrO2 / Al2O3 / ZrO2 / Al2O3 / TiO2 / SiO2), HAHTS(HfO2 / Al2O3 / HfO2 / TiO2 / SiO2), or HAHATS(HfO2 / Al2O3 / HfO2 / Al2O3 / TiO2 / SiO2), but is not limited to these.

[0064] [Silicon-containing film] According to embodiments of the present invention, a silicon-containing film is provided, which is formed using a composition for forming a silicon-containing film comprising a silicon precursor compound represented by Formula 1.

[0065] Silicon-containing films may have a thickness of several nanometers (nm) to several micrometers (μm), and can be applied in various ways depending on the intended purpose.

[0066] In particular, the present invention is characterized by the ability to form silicon-containing films having extremely thin thicknesses of 0.5 nm or less, 0.3 nm or less, 0.2 nm or less, or 0.1 nm to 0.2 nm, which can be used as dielectric films for semiconductor devices.

[0067] A silicon-containing thin film can be formed on a substrate.

[0068] The substrate may be, but is not limited to, a silicon semiconductor wafer, a compound semiconductor wafer, or a plastic substrate (PI, PET, or PES). Furthermore, a substrate having holes or grooves may be used, as may a porous substrate having a large surface area.

[0069] The silicon-containing film according to the embodiment of the present invention is prepared by using a composition for forming a silicon-containing film that contains a silicon precursor compound having a specific structure with excellent thermal stability, and therefore, the silicon-containing film can be efficiently formed by CVD or ALD. In particular, a silicon-containing film with an extremely thin thickness can be uniformly formed in a temperature range of 150°C to 450°C on substrates having patterns (grooves) or fine irregularities on the surface, on porous substrates, or on plastic substrates. This film produces the excellent effect of forming a silicon-containing film with a uniform thickness over the entire surface of the substrate, covering the deepest surface of the patterns (grooves) and the upper surface of the fine irregularities (grooves).

[0070] The silicon-containing film may include at least one selected from the group consisting of silicon-containing oxide films, silicon-containing nitride films, and silicon-containing composite metal oxide films. More specifically, the silicon-containing film may include at least one selected from the group consisting of silicon-containing oxide films and silicon-containing composite metal oxide films.

[0071] [Silicon precursor compounds and methods for preparing them] According to embodiments of the present invention, silicon precursor compounds represented by formula I, more specifically, silicon precursor compounds represented by any one of formulas 5 to 16, may be provided.

[0072] The detailed type and structure of formula I are as described above.

[0073] Furthermore, according to embodiments of the present invention, a silicon precursor compound represented by formula Ia is provided.

[0074] [ka]

[0075] In equation Ia, n is either 0 or 1, and R 1 is hydrogen, R 2 These are independently hydrogen, -SiH3, linear or branched C1-C4 alkyl groups, and -N(R a R b )(wherein, R a and R b Each is independently selected from the group consisting of linear or branched C1-C4 alkyl groups. ) is selected from the group consisting of R 3 ~R 14 Each is independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, provided that R 3 ~R 5 At least one of them is not hydrogen, R 6 ~R 8 At least one of them is not hydrogen.

[0076] More specifically, the silicon precursor compound may be a silicon precursor compound represented by any one of the above formulas 5-12 and 16.

[0077] Because the silicon precursor compound has a specific structure represented by formula I, more specifically by formula Ia, it exhibits excellent thermal stability, and silicon-containing films can be easily formed by CVD or ALD.

[0078] In particular, when a silicon-containing film is formed using a composition for forming a silicon-containing film that includes a silicon precursor compound, the composition can be controlled to achieve a desired film thickness and silicon content, and to form a film with excellent coverage and uniform thickness even on substrates with surface patterns (grooves), porous substrates, plastic substrates, or substrates with complex three-dimensional structures. This makes it possible to provide a high-quality silicon-containing film. Silicon precursor compounds have technical significance in that they can be advantageously used in various applications in the field of electronic devices and can exhibit excellent characteristics.

[0079] On the other hand, according to embodiments of the present invention, a method is provided for preparing a silicon precursor compound represented by the above formula I. The silicon precursor compound represented by formula I can be prepared by various methods.

[0080] A method for preparing a silicon precursor compound according to an embodiment of the present invention comprises subjecting a silicon dihalide precursor compound represented by formula A to a halide-amine substitution reaction with a silyldiamine metal salt represented by formula B.

[0081] [ka]

[0082] In formula A, R 1 and R 2 These are, independently, hydrogen, -SiH3, a linear or branched C1-C4 alkyl group, and -N(R a R b )(wherein, R a and R bEach of the elements is independently selected from the group consisting of linear or branched C1-C4 alkyl groups, and X1 and X2 are each independently halogen elements.

[0083] [ka]

[0084] In equation B, n is 0 or 1, and R 3 ~R 14 Each is independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, provided that R 3 ~R 5 At least one of them is not hydrogen, R 6 ~R 8 At least one of them is not hydrogen, and M1 and M2 are, independently, alkali metals.

[0085] In formula A, X1 and X2 may each be independently Cl, Br, or I, and in formula B, M1 and M2 may each be independently Li or Na.

[0086] In detail, as can be seen from the following reaction scheme 1, the silicon dihalide precursor compound represented by formula A and the silyldiamine metal salt represented by formula B are subjected to a halide-amine substitution reaction for the selective substitution of the amine ligand, and then purified to easily obtain the silicon precursor compound of formula 1.

[0087] [ka]

[0088] In reaction scheme 1, n, R 1 ~R 14 M1, M2, X1, and X2 are as defined above.

[0089] Referring to reaction scheme 1 above, approximately 1 equivalent of a silyldiamine metal salt (formula B) is added to a low-temperature silicon dihalide precursor compound (formula A), and after subjecting it to a halide-amine substitution reaction while maintaining room temperature, the reaction byproduct in the form of a metal halide salt is removed by filtering, and the compound is purified to obtain the silicon precursor compound represented by formula I.

[0090] Furthermore, in the above reaction scheme 1, approximately 1 equivalent of a silyldiamine metal salt (formula B) may be added, approximately 2 equivalents of silyldiamine may be added, or a mixture of 1 to 1.5 equivalents of tetraethylamine (TEA) and silyldiamine may be added.

[0091] Halide-amine substitution reactions can be carried out in solvents at temperatures between -5°C and -30°C.

[0092] Furthermore, the solvent may include one or more selected from the group consisting of alkanes having 5 to 8 carbon atoms, toluene, ethers, tetrahydrofuran, and mono-tetra-ethylene glycol dimethyl ether.

[0093] For example, as can be seen from the following reaction scheme 2, dichlorosilane (SiH2Cl2) and dilithium (N 1 ,N 3 The bis(trimethylsilyl)propane-1,3-diamine) salt is reacted with hexane as a nonpolar solvent at a low temperature of about -10°C to -20°C for about 5 to 30 hours to obtain the silicon precursor compound of formula 8 through a substitution reaction between Cl and the amine.

[0094] [ka]

[0095] In the above reaction scheme 2, dilithium (N 1 ,N 3 -Bis(trimethylsilyl)propane-1,3-diamine) is made of n-BuLi and N 1 ,N 3It can be prepared by reacting -bis(trimethylsilyl)propane-1,3-diamine with hexane, a nonpolar solvent, at low temperature.

[0096] In reaction scheme 2, it is preferable to carry out the reaction under a flow of nitrogen (N2) or argon (Ar) in order to safely remove the reaction products, namely the salt (LiCl) and unreacted dichlorosilane (SiH2Cl2), and to suppress decomposition reactions that occur during the reaction due to moisture or oxygen. (Mode of the Invention)

[0097] The present invention will be described in detail below with reference to examples. The following examples are for illustrative purposes only and the scope of the present invention is not limited thereto. [Examples]

[0098] <Preparation example 1>N 1 ,N 2 Preparation of bis(trimethylsilyl)ethane-1,2-diamine [ka]

[0099] Approximately 450 g (approximately 4.1421 mol) of trimethylsilyl chloride and approximately 2,500 ml of diethyl ether were mixed in a 5-liter round-bottom flask. Approximately 248.94 g (approximately 4.1421 mol) of ethylenediaminelysine was slowly added to the reaction system at approximately -20°C, and the temperature was then gradually raised to room temperature while stirring, followed by stirring for approximately 17 hours. After the reaction was complete, the salt formed during the reaction was removed by filtration, and the solvent and volatile by-reactants were removed by vacuum distillation to obtain approximately 348.18 g (yield approximately 82.2%) of N2. 1 ,N 2 -Bis(trimethylsilyl)ethane-1,2-diamine [{(CH3)3Si}HNCH2CH2NH{Si(CH3)3}] was obtained as a colorless liquid compound represented by formula 2.

[0100] Boiling point: 73°C at 10 Torr (196°C at 760 Torr) 1 H-NMR (C6D6): δ0.092 (N-Si-CH * 3, s, 18H), δ2.599, 2.579 (N-CH * 2, m, 4H)

[0101] <Preparation Example 2> N 1 , N 3 -Bis(trimethylsilyl)propane-1,3-diamine Preparation

Chemical formula

[0102] Approximately 395.69 g (approximately 3.6425 mol) of trimethylsilyl chloride and approximately 2,000 ml of diethyl ether were mixed in a 5-liter round-bottom flask. Approximately 270 g (approximately 3.6425 mol) of 1,3-diaminopropane was slowly added to the reaction system at approximately -2C, and then the temperature was gradually raised to room temperature while stirring, followed by stirring for approximately 17 hours. After the reaction was complete, the salt formed during the reaction was removed by filtration, and the solvent and volatile side reaction substances were removed by distillation under reduced pressure to obtain approximately 309 g (yield approximately 77.6%) of N 1 , N 3 -Bis(trimethylsilyl)propane-1,3-diamine [{(CH3)3Si}HNCH2CH2CH2NH{Si(CH3)3}] as a colorless liquid compound represented by Formula 3 was obtained.

[0103] Boiling point: 80 C at 10 Torr (204 C at 760 Torr) 1 H-NMR (C6D6): δ0.095 (N-Si-CH * 3, s, 18H), δ1.386 (N-CH2-CH * 2, m, 2H), δ2.703, 2.684 (N-CH * 2-CH2, m, 4H)

[0104] <Preparation Example 3> N 1 , N 2 -Bis(trimethylsilyl)propane-!2-diamine Preparation [ka]

[0105] Approximately 350 g (approximately 3.2216 moles) of trimethylsilyl chloride and approximately 2,000 ml of diethyl ether were mixed in a 3-liter round-bottom flask. Approximately 238.82 g (approximately 3.2216 moles) of 1,2-diaminopropane was slowly added to the reaction system at approximately -20°C, and the temperature was then gradually raised to room temperature while stirring, followed by stirring for approximately 17 hours. After the reaction was complete, the salt formed during the reaction was removed by filtration, and the solvent and volatile by-reactants were removed by vacuum distillation to obtain approximately 279 g (yield approximately 79.1%) of N2. 1 ,N 2 -Bis(trimethylsilyl)propane-1,2-diamine [{(CH3)3Si}HNCH(CH3)CH2NH{Si(CH3)3}] was obtained as a colorless liquid compound represented by formula 4.

[0106] Boiling point: 78°C at 10 Torr (202°C at 760 Torr) 1 H-NMR(C6D6):δ0.091,0.102(N-Si-CH * 3,d,18H),δ0.921,0.936(N-CH-CH * 3,d,3H),δ2.461(N-CH * 2,m,2H),δ2.636,2.651(N-CH * ,m,1H)

[0107] <Example 1> Preparation of N,N-dimethyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopenta-2-amine and a composition for forming a silicone-containing film containing the same. [ka]

[0108] Approximately 265.55 g (2.5 M, approximately 0.953 mol) of n-butyllithium hexane solution (n-BuLi in n-hexane) was mixed with approximately 2,000 ml of anhydrous hexane in a 5 liter round-bottom flask. Approximately 97.47 g (approximately 0.4767 mol) of N obtained in Preparation Example 1 was used. 1 ,N 2 -Bis(trimethylsilyl)ethane-1,2-diamine was slowly added to the reaction system at approximately -20°C, and then the temperature was gradually raised to room temperature while stirring, followed by 4 hours of stirring. Approximately 64.56 g (approximately 0.4767 mol) of trichlorosilane was added to the dilithium(N) solution formed in this manner at approximately -20°C. 1 ,N 2 The solution was slowly added to the bis(trimethylsilyl)ethane-1,2-diamine salt solution, and then the temperature was gradually raised to room temperature while stirring, followed by stirring for 4 hours to form a 2-chloro-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopentane solution.

[0109] Meanwhile, approximately 119.48 g (2.5 M, approximately 0.429 mol) of n-butyllithium hexane solution (n-BuLi in n-hexane) was mixed with approximately 500 ml of anhydrous hexane in another 1 liter round-bottom flask. Approximately 19.34 g (approximately 0.429 mol) of dimethylamine was slowly added to the above mixture at approximately -20°C, and the temperature was then gradually raised to room temperature while stirring, followed by stirring for approximately 4 hours. The lithium dimethyl salt solution thus formed was slowly added to a 2-chloro-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopentane solution at approximately -20°C, and the temperature was then gradually raised to room temperature, followed by stirring for 17 hours. After the reaction was complete, the salt formed during the reaction was removed by filtration, and the solvent and volatile by-reactants were removed by vacuum distillation to obtain 84.1 g (yield approximately 64.1%) of N,N-dimethyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopenta-2-amine [{((CH3)3Si)NCH2CH2N(Si(CH3)3)}SiH{N(CH3)2}] as a colorless liquid compound represented by formula 5, which was used in a composition for forming a film.

[0110] Boiling point: 36°C at 0.3 Torr (217°C at 760 Torr) 1 H-NMR (C6D6):δ0.157(N-Si-CH * 3,s,18H),δ2.404(Si-N-CH * 3,s,6H),δ2.942,2.864(N-CH * 2,m,4H),δ4.832(Si-H * ,s,1H)

[0111] <Example 2> Preparation of N,N-dimethyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclohexane-2-amine and a composition for forming a silicone-containing film containing the same. [ka]

[0112] Approximately 92.9 g (yield approximately 62.8%) of N,N-dimethyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclohexane-2-amine [{((CH3)3Si)NCH2CH2CH2N(Si(CH3)3)}SiH{N(CH3)2}] was used as a colorless liquid compound represented by formula 6, as obtained in Preparation Example 1. 1 ,N 2 -Instead of bis(trimethylsilyl)ethane-1,2-diamine, use the N obtained in Preparation Example 2. 1 ,N 3 -The same method as in Example 1 was used, except that bis(trimethylsilyl)propane-1,3-diamine was used, and this was then used in a composition for forming a film.

[0113] Boiling point: 46°C at 0.3 Torr (233°C at 760 Torr) 1 H-NMR (C6D6):δ0.162(N-Si-CH * 3,s,18H),δ1.495,1.479(N-CH2-CH * 2,m,2H),δ2.451(Si-N-CH *3,s,6H),δ2.914,2.926(N-CH * 2-CH2,m,4H),δ4.743(Si-H * ,s,1H)

[0114] <Example 3> Preparation of 1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopentane and a composition for forming a silicone-containing film containing the same. [ka]

[0115] Approximately 275.74 g (2.5 M, approximately 0.990 mol) of n-butyllithium hexane solution (n-BuLi in n-hexane) was mixed with approximately 2,000 ml of anhydrous hexane in a 5 liter round-bottom flask. Approximately 101.22 g (approximately 0.495 mol) of N obtained in Preparation Example 1 was then mixed. 1 ,N 2 -Bis(trimethylsilyl)ethane-1,2-diamine was slowly added to the reaction system at approximately -20°C, and then the temperature was gradually raised to room temperature while stirring, followed by stirring for approximately 4 hours. Approximately 50 g (approximately 0.495 mol) of dichlorosilane was added to the dilithium (N) dilithium (N) dichlorosilane thus formed at approximately -20°C. 1 ,N 2 The bis(trimethylsilyl)ethane-1,2-diamine) salt solution was slowly added, and the temperature was gradually raised to room temperature while stirring, followed by stirring for approximately 17 hours. Once the reaction was complete, the salt formed during the reaction was removed by filtration, and the solvent and volatile by-reactants were removed by vacuum distillation to obtain approximately 68.3 g (yield approximately 59.4%) of 1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopentane [{((CH3)3Si)NCH2CH2N(Si(CH3)3)}SiH2] as a colorless crystalline solid compound represented by formula 7, which was used in a composition for forming a film.

[0116] Boiling point: 76°C at 10 Torr (200°C at 760 Torr) 1 H-NMR (C6D6):δ0.160(N-Si-CH* 3,s,18H),δ2.848(N-CH * 2,s,4H),δ5.169(Si-H * ,s,2H)

[0117] <Example 4> Preparation of 1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclohexane and a composition for forming a silicone-containing film containing the same. [ka]

[0118] Approximately 69.3 g (yield approximately 61.9%) of 1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclohexane[{((CH3)3Si)NCH2CH2CH2N(Si(CH3)3)}SiH2] was used as a colorless liquid compound represented by formula 8, and the N obtained in Preparation Example 1 was used. 1 ,N 2 -Instead of bis(trimethylsilyl)ethane-1,2-diamine, use the N obtained in Preparation Example 2. 1 ,N 3 -The same method as in Example 3 was used, except that bis(trimethylsilyl)propane-1,3-diamine was used, and this was then used in a composition for forming a film.

[0119] Boiling point: 87°C at 10 Torr (213°C at 760 Torr) 1 H-NMR (C6D6):δ0.145(N-Si-CH * 3,s,18H),δ1.411(N-CH2-CH * 2,m,2H),δ2.915(N-CH * 2-CH2,m,4H),δ5.143(Si-H * ,s,2H)

[0120] <Example 5> Preparation of 4-methyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopentane and a composition for forming a silicone-containing film containing the same. [ka]

[0121] Approximately 87.9 g (yield approximately 72%) of 4-methyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopentane [{((CH3)3Si)NCH(CH3)CH2N(Si(CH3)3)}SiH2] was used as the colorless liquid compound represented by formula 9, and the N obtained in Preparation Example 1 was used. 1 ,N 2 -Instead of bis(trimethylsilyl)ethane-1,3-diamine, use the N obtained in Preparation Example 3. 1 ,N 2 -The same method as in Example 3 was used, except that bis(trimethylsilyl)propane-1,2-diamine was used, and this was then used in a composition for forming a film.

[0122] Boiling point: 95°C at 10 Torr (223°C at 760 Torr) 1 H-NMR(C6D6):δ0.159,0.172(N-Si-CH * 3,d,18H),δ1.002,1.018(N-CH-CH * 3,d,3H),δ2.571,2.552(N-CH * 2,q,1H),δ2.971,2.960(N-CH * 2,q,1H),δ3.269,3.275(N-CH * -CH3,m,1H),δ5.174,5.181(Si-H * ,d,2H)

[0123] <Example 6> Preparation of 2-methyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopentane and a composition for forming a silicone-containing film containing the same. [ka]

[0124] Approximately 163.47 g (2.5 M, approximately 0.587 mol) of n-butyllithium hexane solution (n-BuLi in n-hexane) was mixed with approximately 1,000 ml of anhydrous hexane in a 3 liter round-bottom flask. Approximately 60 g (approximately 0.2935 mol) of N obtained in Preparation Example 1 was then mixed. 1 ,N 2 -Bis(trimethylsilyl)ethane-1,2-diamine was slowly added to the reaction system at approximately -20°C, and then the temperature was gradually raised to room temperature while stirring, followed by 4 hours of stirring. Approximately 33.76 g (approximately 0.2934 mol) of dichloromethylsilane was added to the dilithium(N) solution formed in this manner at approximately -20°C. 1 ,N 2 The bis(trimethylsilyl)ethane-1,2-diamine) salt solution was slowly added, and the temperature was gradually raised to room temperature while stirring, followed by stirring for approximately 17 hours. Once the reaction was complete, the salt formed during the reaction was removed by filtration, and the solvent and volatile by-reactants were removed by vacuum distillation to obtain approximately 50 g (yield approximately 69.1%) of 2-methyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopentane [{((CH3)3Si)NCH2CH2N(Si(CH3)3)}SiH(CH3)] as a colorless liquid compound represented by formula 10, which was used in a composition for forming a film.

[0125] Boiling point: 81°C at 10 Torr (205°C at 760 Torr) 1 H-NMR (C6D6):δ0.150(N-Si-CH * 3,s,18H),δ0.254,0.259(Si-CH * 3,d,3H),δ2.890(N-CH * 2,s,4H),δ5.215,5.219(Si-H * ,d,1H)

[0126] <Example 7> Preparation of 2-methyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclohexane and a composition for forming a silicone-containing film containing the same. [ka]

[0127] Approximately 51.8 g (yield approximately 66.3%) of 2-methyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclohexane [{((CH3)3Si)NCH2CH2CH2N(Si(CH3)3)}SiH(CH3)] was used as a colorless liquid compound represented by formula 11, as obtained in Preparation Example 1. 1 ,N 2 -Instead of bis(trimethylsilyl)ethane-1,2-diamine, use the N obtained in Preparation Example 2. 1 ,N 3 -The same method as in Example 6 was used, except that bis(trimethylsilyl)propane-1,3-diamine was used, and this was then used in a composition for forming a film.

[0128] Boiling point: 40°C at 0.3 Torr (223°C at 760 Torr) 1 H-NMR (C6D6):δ0.147(N-Si-CH * 3,s,18H),δ0.283,0.289(Si-CH * 3,d,3H),δ1.408,1.417(N-CH2-CH * 2,m,1H),δ1.475,1.485(N-CH2-CH * 2,m,1H),δ2.906,2.914(N-CH * 2,m,4H),δ5.046(Si-H * ,d,1H)

[0129] <Example 8> Preparation of a composition for forming a silicone-containing film containing 2,4-dimethyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopentane. [ka]

[0130] Approximately 61 g (yield approximately 59.8%) of 2,4-dimethyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopentane [{((CH3)3Si)NCH(CH3)CH2N(Si(CH3)3)}SiH(CH3)] was used as a colorless liquid compound represented by formula 12, as obtained in Preparation Example 1. 1 ,N 2 -Instead of bis(trimethylsilyl)ethane-1,2-diamine, use the N obtained in Preparation Example 3. 1 ,N 2 -The same method as in Example 6 was used, except that bis(trimethylsilyl)propane-1,2-diamine was used, and this was then used in a composition for forming a film.

[0131] Boiling point: 45°C at 0.3 Torr (230°C at 760 Torr) 1 H-NMR(C6D6):δ0.154,0.157(N-Si-CH * 3,q,18H),δ0.251,0.304(Si-CH * 3,q,3H),δ1.043(N-CH-CH * 3,t,3H),δ2.578,3.019(N-CH * 2,m,2H),δ3.265,3.280(N-CH * ,m,1H),δ5.205,5.232(Si-H * ,d,1H)

[0132] <Example 9> Preparation of 2,2-dimethyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopentane and a composition for forming a silicone-containing film containing the same. [ka]

[0133] Approximately 302.12 g (2.5 M, approximately 1.084 mol) of n-butyllithium hexane solution (n-BuLi in n-hexane) was mixed with approximately 2,000 ml of anhydrous hexane in a 5 liter round-bottom flask. Approximately 110.89 g (approximately 0.542 mol) of N obtained in Preparation Example 1 was mixed.1 ,N 2 -Bis(trimethylsilyl)ethane-1,2-diamine was slowly added to the reaction system at approximately -20°C, and then the temperature was gradually raised to room temperature while stirring, followed by stirring for approximately 4 hours. Approximately 70 g (approximately 0.542 mol) of dichlorodimethylsilane was added to the dilithium(N) 1 ,N 2 The bis(trimethylsilyl)ethane-1,2-diamine) salt solution was slowly added, and the temperature was gradually raised to room temperature while stirring, followed by stirring for approximately 17 hours. Once the reaction was complete, the salt formed during the reaction was removed by filtration, and the solvent and volatile by-reactants were removed by vacuum distillation to obtain approximately 89.5 g (yield approximately 63.3%) of 2,2-dimethyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopentane[{((CH3)3Si)NCH2CH2N(Si(CH3)3)}Si(CH3)2] as a colorless liquid compound represented by formula 13, which was used in a composition for forming a film.

[0134] Boiling point: 35°C at 0.3 Torr (216°C at 760 Torr) 1 H-NMR (C6D6):δ0.139(N-Si-CH * 3,s,18H),δ0.235(Si-CH * 3,s,6H),δ2.904(N-CH * 2, s, 4H)

[0135] <Example 10> Preparation of 2,2-dimethyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclohexane and a composition for forming a silicone-containing film containing the same. [ka]

[0136] Approximately 109.4 g (yield approximately 64.4%) of 2,2-dimethyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclohexane[{((CH3)3Si)NCH2CH2CH2N(Si(CH3)3)}Si(CH3)2] was used as a colorless liquid compound represented by formula 14, and the N obtained in Preparation Example 1 was used. 1 ,N 2 -Instead of bis(trimethylsilyl)ethane-1,2-diamine, use the N obtained in Preparation Example 2. 1 ,N 3 -The same method as in Example 9 was used, except that bis(trimethylsilyl)propane-1,3-diamine was used, and this was then used in a composition for forming a film.

[0137] Boiling point: 44°C at 0.3 Torr (229°C at 760 Torr) 1 H-NMR (C6D6):δ0.139(N-Si-CH * 3,s,18H),δ0.281(Si-CH * 3,s,6H),δ1.463(N-CH2-CH * 2,m,2H),δ2.935(N-CH * 2,t,4H)

[0138] <Example 11> Preparation of 2,2-dimethyl-1,3-bis(dimethylsilyl)-1,3-diaza-2-silacyclopentane and a composition for forming a silicone-containing film containing the same. [ka]

[0139] Approximately 54.27 g (approximately 0.903 mol) of ethylenediamine, approximately 1,000 ml of anhydrous hexane, and approximately 800 ml of diethyl ether were mixed in a 3-liter round-bottom flask. Approximately 116.54 g (approximately 0.903 mol) of dichlorodimethylsilane was slowly added to the above mixture at approximately -20°C, and the temperature was then gradually raised to room temperature while stirring, followed by stirring for approximately 17 hours. After the reaction was complete, the salt formed during the reaction was removed by filtration, and the solvent and volatile by-reactants were removed by vacuum distillation to obtain approximately 46.4 g (yield approximately 64.1%) of 2,2-dimethyl-1,3-bis(dimethylsilyl)-1,3-diaza-2-silacyclopentane[{((CH3)2SiCl)NCH2CH2N(ClSi(CH3)2)}Si(CH3)2] as a white solid compound.

[0140] In addition, approximately 4.08 g (approximately 0.1077 mol) of lithium aluminum hydride, approximately 200 ml of anhydrous hexane, and approximately 200 ml of diethyl ether were mixed in a separate 2-liter round-bottom flask. Approximately 46.4 g (approximately 0.903 mol) of the 2,2-dimethyl-1,3-bis(chlorodimethylsilyl)-1,3-diaza-2-silacyclopentane obtained above was slowly added to the mixture at approximately -20°C, and the temperature was then gradually raised to room temperature while stirring, followed by stirring for approximately 17 hours. After the reaction was complete, the salt formed during the reaction was removed by filtration, and the solvent and volatile by-reactants were removed by vacuum distillation to obtain approximately 42.4 g (yield approximately 64.2%) of 2,2-dimethyl-1,3-bis(dimethylsilyl)-1,3-diaza-2-silacyclopentane [{((CH3)2SiH)NCH2CH2N(HSi(CH3)2)}Si(CH3)2] as a colorless liquid compound represented by formula 15, which was used in a composition for forming a film.

[0141] Boiling point: 77°C at 10 Torr (201°C at 760 Torr) 1 H-NMR(C6D6):δ0.156,0.163(N-Si-CH * 3,d,12H),δ0.230(Si-CH * 3,s,6H),δ2.899(N-CH* 2,s,4H),δ4.756(N-Si-H * ,m,2H)

[0142] <Example 12> Preparation of 4-methyl-2-silyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopentane and a composition for forming a silicone-containing film containing the same. [ka]

[0143] Approximately 217.5 g (2.5 M, approximately 0.7809 mol) of n-butyllithium hexane solution (n-BuLi in n-hexane) was mixed with approximately 1,500 ml of anhydrous hexane in a 3 liter round-bottom flask. Approximately 85.3 g (approximately 0.3905 mol) of N obtained in Preparation Example 3 was used. 1 ,N 2 -Bis(trimethylsilyl)propane-1,2-diamine was slowly added to the above mixture at approximately -20°C, and then the temperature was gradually raised to room temperature while stirring, followed by stirring for approximately 4 hours. Approximately 105 g (approximately 0.3905 mol) of hexachlorodisilane was added to the dilithium (N) mixture thus formed at approximately -20°C. 1 ,N 2 The bis(trimethylsilyl)propane-1,2-diamine) salt solution was slowly added, and the temperature was gradually raised to room temperature while stirring, followed by stirring for approximately 17 hours. Once the reaction was complete, the salt formed during the reaction was removed by filtration, and the solvent and volatile by-reactants were removed by vacuum distillation to obtain approximately 134 g (yield approximately 82.9%) of 2-chloro-4-methyl-2-(trichlorosilyl)-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopentane [{((CH3)3Si)NCH(CH)3CH2N(Si(CH3)3)}SiClSiCl3] as a colorless liquid compound.

[0144] Meanwhile, approximately 17.18 g (approximately 0.4528 mol) of lithium aluminum hydride, approximately 600 ml of anhydrous hexane, and approximately 200 ml of diethyl ether were mixed in a separate 2-liter round-bottom flask. Approximately 134.04 g (approximately 0.3234 mol) of the above-prepared 2-chloro-4-methyl-2-(trichlorosilyl)-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopentane was slowly added to the mixture at approximately -20°C, and the temperature was then gradually raised to room temperature while stirring, followed by stirring for approximately 17 hours. After the reaction was complete, the salt formed during the reaction was removed by filtration, and the solvent and volatile by-reactants were removed by vacuum distillation to obtain approximately 58.7 g (yield approximately 65.6%) of 4-methyl-2-silyl-1,3-bis(trimethylsilyl)-1,3-diaza-2-silacyclopentane [{((CH3)3Si)NCH(CH)3CH2N(Si(CH3)3)}SiHSiH3] as a colorless liquid compound represented by formula 16, which was used in a composition for forming a film.

[0145] Boiling point: 49°C at 0.3 Torr (236°C at 760 Torr) 1 H-NMR (C6D6):δ0.166(N-Si-CH * 3,t,18H),δ0.988,0.996(N-CH-CH * 3,q,3H),δ2.564(N-CH * 2,t,1H),δ2.930,2.942,2.971(N-CH * 2,m,1H),δ3.205,3.303(N-CH * -CH3,m,1H),δ3.376,3.414(Si-H * ,q,3H),δ5.698,5.730(Si-H * ,d,1H))

[0146] Comparative Example 1 Tris(dimethylamide)silane (3DMAS or TDMAS) [SiH(NMe2)3] (manufactured by UP Chemical Co., Ltd.) was used.

[0147] Comparative Example 2 Tris(pyrrolidino)silane (TPYS)[SiH[N(CH2)4]3 (manufactured by UP Chemical Co., Ltd.), in which cyclic amine pyrrolidine is substituted for dimethylamine, was used.

[0148] [Test Examples] <Test Example 1> Thermogravimetric Analysis of Silicon Precursor Compounds Thermogravimetric analysis (TGA) was performed on the silicon precursor compounds prepared in Examples 1, 4, 5, 6, and 9 of the above examples, and the results are shown in Figure 2.

[0149] As can be seen from Figure 2, the silicon precursor compounds prepared in Examples 1, 4, 5, 6, and 9 volatilize with almost no residue, making them suitable for forming silicon-containing films by chemical vapor deposition or atomic layer deposition.

[0150] <Test Example 2> ALD deposition using a composition for forming a silicon-containing film An SiO2 film was formed by ALD using a composition for forming a silicon-containing film, each containing the silicon precursor compound of Examples 1, 4, 5, 6, and 9, and ozone (O3) as the reaction gas.

[0151] In detail, each of the film-forming compositions was placed in a stainless steel container. The film-forming compositions were supplied in gaseous form to the ALD reactor (reaction chamber) by flowing argon (Ar) transport gas at a flow rate of approximately 200 sccm. The stainless steel containers containing the compositions for forming silicon-containing films, each containing the silicon precursor compounds of Comparative Example 1 and Example 6, were maintained at room temperature. The stainless steel containers containing the compositions for forming silicon-containing films, each containing the silicon precursor compounds of Examples 4, 5, and 9, were maintained at 40°C. The stainless steel container containing the composition for forming silicon-containing films, each containing the silicon precursor compound of Example 1, was maintained at 60°C. The stainless steel container containing the composition for forming silicon-containing films, each containing the silicon precursor compound of Comparative Example 2, was heated to 95°C for use.

[0152] Meanwhile, the silicon substrate was immersed for 10 minutes in a piranha solution, which was a mixture of sulfuric acid (H2SO4) and hydrogen peroxide (H2O2) in a 4:1 ratio, and then removed. Next, it was immersed for 2 minutes in a diluted aqueous HF solution to form a silicon surface from which the untreated oxide film had been removed. Then, an SiO2 film was formed by ALD using a composition for forming a silicon-containing film that contained a silicon precursor compound. Here, the process pressure of the ALD reactor was maintained at 1 Torr, and the silicon substrate was heated to temperatures of 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, and 450°C.

[0153] The following ALD gas supply cycle was repeated 100 times to form an SiO2 film: the composition for forming the silicon film was supplied in gaseous form for approximately 3 seconds; argon (Ar) gas was supplied for approximately 10 seconds to remove any remaining film-forming composition (gas) in the reactor; ozone (O3) was supplied as a reaction gas for approximately 5 seconds; and argon (Ar) gas was supplied for approximately 10 seconds to remove any remaining ozone (O3) in the reactor.

[0154] To measure the deposition rate (GPC) under ALD gas supply, the thickness of the SiO2 film formed in this manner was measured using an elliptic polarimeter (Nano View SEMG-1000). The results are shown in Table 1 and Figure 2 below.

[0155] [Table 1]

[0156] As can be seen from Table 1 and FIG. 1, when ALD deposition was carried out using a composition for forming a silicon-containing film containing each of the silicon precursor compounds of Examples 1, 4, 5, 6, and 9, the film formation rate of the ALD gas supply was significantly lower than that of Comparative Examples 1 and 2. In particular, when the composition for forming a silicon-containing film containing the silicon precursor compound of the present invention was used at about 300 °C, which is the temperature for forming a capacitor dielectric film or a dielectric film of DRAM, the film formation rate of the ALD gas supply was very low, about 0.15 to 0.20 Å / cycle.

[0157] In contrast, when a composition for forming a silicon-containing film containing the silicon precursor compound (3DMAS) of Comparative Example 1 was used, the film formation rate of the ALD gas supply for the SiO2 film was 0.48 Å / cycle. When a composition for forming a silicon-containing film containing the silicon precursor compound of Comparative Example 2 was used, the film formation rate of the ALD gas supply for the SiO2 film was 0.51 Å / cycle. When a composition for forming a silicon-containing film containing the silicon precursor compound of the example of the present invention was used, the GPC was about 2 / 5.

[0158] Also, when a composition for forming a silicon-containing film containing the silicon precursor compound of Comparative Example 1 or 2 was used, the SiO2 film could be adjusted only at increments of 0.5 Å / cycle, for example, at 0.5, 1.0, and 1.5 Å / cycle. In contrast, when a composition for forming a silicon-containing film containing the silicon precursor compound of the present invention was used, the film thickness could be adjusted at an increment of about 0.2 Å / cycle, and the SiO2 film thickness could be accurately adjusted 2.5 times.

Claims

1. A silicon precursor compound represented by formula I-a. 【Chemistry 1】 [In Formula I-a, n is 0 or 1, and R １ is hydrogen, and R ２ is hydrogen, -SiH ３ a linear or branched C １ to C ４ alkyl group, and -N(R ａ R ｂ )(wherein, R ａ and R ｂ are each independently selected from the group consisting of linear or branched C １ to C ４ alkyl groups). R is selected from the group consisting of ３ to R １４ are each independently hydrogen and a linear or branched C １ to C ４ alkyl group, provided that at least one of R ３ to R ５ is not hydrogen, and at least one of R ６ to R ８ is not hydrogen.]

2. A silicon precursor compound according to claim 1, represented by any one of formulas 5 to 12 and 16. 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】

3. A composition for forming a silicon-containing film, comprising a silicon precursor compound represented by formula I. 【Chemistry 11】 [In formula I, n is 0 or 1, R １ and R ２ These are, independently, hydrogen and -SiH. ３ , linear or branched C １ ~C ４ Alkyl alkyl groups, and -N(R ａ R ｂ ) (wherein, R ａ and R ｂ Each of these is independently linear or branched C １ ~C ４ Selected from the group consisting of alkyl groups. ) Selected from the group consisting of R ３ ~R １４ These are, independently, hydrogen and linear or branched carbon atoms. １ ~C ４ Selected from the group consisting of alkyl groups, however, R ３ ~R ５ At least one of them is not hydrogen, R ６ ~R ８ At least one of them is not hydrogen.

4. A composition for forming a silicon-containing film according to claim 3, comprising a silicon precursor compound represented by any one of formulas 5 to 16. 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 【Chemistry 23】

5. A method for forming a silicon-containing film, comprising using a composition for forming a silicon-containing film, comprising a silicon precursor compound represented by formula I. 【Chemistry 24】 [In formula I, n is 0 or 1, R １ and R ２ These are, independently, hydrogen and -SiH. ３ , linear or branched C １ ~C ４ Alkyl alkyl groups, and -N(R ａ R ｂ ) (wherein, R ａ and R ｂ Each of these is independently linear or branched C １ ~C ４ Selected from the group consisting of alkyl groups. ) Selected from the group consisting of R ３ ~R １４ These are, independently, hydrogen and linear or branched carbon atoms. １ ~C ４ Selected from the group consisting of alkyl groups, however, R ３ ~R ５ At least one of them is not hydrogen, R ６ ~R ８ At least one of them is not hydrogen.

6. A method for forming the silicon-containing film according to claim 5, wherein the silicon-containing film is formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

7. The silicon-containing film comprises at least one selected from the group consisting of silicon-containing oxide films and silicon-containing composite metal oxide films. A method for forming a silicon-containing film according to claim 5, wherein, when the film is formed by a deposition method, an oxygen source is used that includes at least one selected from the group consisting of water vapor, oxygen, oxygen plasma, nitrogen oxide, nitrogen oxide plasma, hydrogen peroxide, and ozone.

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