Trisilylamine compound, silicon-containing thin film deposition composition containing the same, and method for producing a silicon-containing thin film using the same.

Abstract

The present invention provides a silicon-containing thin film produced from a trisilylamine compound that exhibits excellent chemical and thermal stability, has a low dielectric constant, and is usefully applicable as an insulating film for semiconductor devices, particularly as a spacer in semiconductor miniaturization processes; a silicon-containing thin film deposition composition containing the same; and a method for producing a silicon-containing thin film using the same. [Solution] The silicon-containing thin film produced from the trisilylamine compound according to the present invention is represented by chemical formula 1. JPEG2026069760000037.jpg22170 In chemical formula 1, R1 to R7 are each independently hydrogen, a C1-C7 alkyl group, or a fluoro group.

Description

[Technical Field]

[0001] The present invention relates to a trisilylamine compound that can be used as a precursor for silicon thin films, a silicon-containing thin film deposition composition containing the same, and a method for producing a silicon-containing thin film using the same. [Background technology]

[0002] The performance and reliability of semiconductor devices are largely dependent on the electrical and mechanical properties of the various materials within the device. In particular, the insulating film within a semiconductor device plays a crucial role in reducing signal interference and stabilizing the device's electrical characteristics. Therefore, various techniques are being researched to improve the physical and chemical properties of insulating films.

[0003] While silicon oxide and silicon nitride films, commonly used as insulating film materials, offer excellent insulating properties, the miniaturization of advanced devices is creating a need for new insulating materials with lower dielectric constants. Lower dielectric constants improve device performance and reduce electrical interference (capacitance) during signal transmission. To address these demands, fluorine-doped silicon thin films are attracting attention. Fluorine possesses high electronegativity, and when doped into silicon thin films, it can lower the dielectric constant of the insulating film, significantly improving the electrical performance of the device. Furthermore, fluorine doping plays a crucial role in reducing charge trapping in the insulating film, enhancing long-term reliability, strengthening resistance to moisture, and preventing performance degradation due to external environmental factors.

[0004] However, precursors for forming silicon thin films containing fluorine are still in the development stage, and a stable and efficient deposition process is required. Conventional precursors have limitations in forming a uniform thin film while maintaining a stable fluorine content. A method of doping fluorine (F) after forming the silicon thin film has been proposed, but this involves an additional fluorine doping step, making the process complex. There are limitations in that doping mainly proceeds only near the surface of the thin film, resulting in a decrease in the quality of the thin film.

[0005] Therefore, there is a need to develop a new precursor that can more effectively deposit a silicon thin film containing fluorine.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] One aspect of the present invention provides a trisilylamine compound that can be used as a high-quality low dielectric thin film precursor, and a composition for depositing a silicon-containing thin film containing the same.

[0008] Another aspect of the present invention provides a manufacturing method capable of manufacturing a silicon-containing thin film at a high deposition rate and capable of manufacturing a high-quality thin film with a high yield.

Means for Solving the Problems

[0009] One aspect of the present invention provides a trisilylamine compound represented by the following Chemical Formula 1.

[0010] [Chemical Formula 1]

Chem.

[0011] Said R 1 , R 4 , and R 6 are each independently hydrogen or fluoro, and R 2 , R 3 , R 5 , and R 7 may each independently be hydrogen, C1-C7 alkyl, or fluoro.)

[0012] The trisilylamine compound according to one aspect may be represented by the following Chemical Formula 2.)

[0013] [Chemical Formula 2]

Chem.

[0014] Said R 1 is hydrogen or fluoro, and R 2 and R 3 are each independently hydrogen, C1-C7 alkyl, or fluoro, and R 11 may be C1-C7 alkyl or fluoro.)

[0015] The trisilylamine compound according to one aspect may be selected from the following structures.)

Chem.

[0016] Another aspect of the present invention provides a silicon-containing thin film deposition composition comprising the trisilylamine compound.

[0017] A further aspect of the present invention provides a silicon-containing thin film produced from a trisilylamine compound represented by the following chemical formula 1, or a thin film deposition composition containing the same.

[0018] [Chemical formula 1] [ka] (In the above chemical formula 1, R 1 ~R 7 These are, independently, hydrogen, C1-C7 alkyl, or fluoro.

[0019] A further aspect of the present invention provides a method for producing a silicon-containing thin film using a trisilylamine compound represented by the following chemical formula 1, or a thin film deposition composition containing the same, and a reaction gas.

[0020] [Chemical formula 1] [ka] (In the above chemical formula 1, R 1 ~R 7 These are, independently, hydrogen, C1-C7 alkyl, or fluoro.

[0021] The reaction gas may include oxygen (O2), ozone (O3), oxygen plasma, hydrogen (H2), hydrogen plasma, water (H2O), hydrogen peroxide (H2O2), nitrogen (NO2), nitric oxide (NO), nitrous oxide (N2O), ammonia (NH3), carbon dioxide (CO2), formic acid (HCOOH), acetic acid (CH3COOH), acetic anhydride ((CH3CO)2O), or a combination thereof.

[0022] The reaction gas may further contain hydrocarbon gases. [Effects of the Invention]

[0023] A trisilylamine compound according to one aspect of the present invention exhibits excellent thermal stability, allowing for the deposition of thin films with a high thin-film deposition rate even under low temperature conditions, and enabling the production of high-quality silicon-containing thin films with high purity through a simple manufacturing process.

[0024] Furthermore, silicon-containing thin films produced from a trisilylamine compound according to one embodiment are expected to be usefully applicable as insulating films for semiconductor devices, particularly as spacers in semiconductor miniaturization processes, because they not only exhibit excellent chemical and thermal stability but also have a low dielectric constant. [Brief explanation of the drawing]

[0025] [Figure 1] These are the TGA and DSC analysis results for bis(fluoromethylsilyl)methylsilylamine produced in Example 1. [Modes for carrying out the invention]

[0026] Unless otherwise defined herein, all technical and scientific terms have the same meanings as those generally understood by those skilled in the art to which this invention belongs. The terms used in this description are for the effective purpose of describing specific examples and are not intended to limit the invention.

[0027] In this invention, the singular form is intended to include multiple forms unless otherwise specified in the context.

[0028] Throughout this specification, the terms "includes," "companies," "contains," or "has" a component mean, unless otherwise stated, that it may include other components rather than excluding them, and do not exclude any elements, materials, or processes not specifically mentioned.

[0029] As used herein, numerical ranges include lower and upper limits, all values ​​within those ranges, increments logically derived from the form and width of the defined range, all double-limited values, and all possible combinations of upper and lower limits of numerical ranges limited in different forms. Unless otherwise defined in the specification of the present invention, values ​​outside the numerical range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0030] Unless otherwise defined herein, “approximately” may refer to values ​​up to 30%, 25%, 20%, 15%, 10%, or 5% of the specified value.

[0031] As used herein, the term “alkyl” refers to an organic radical derived from an aliphatic hydrocarbon by the removal of one hydrogen atom, and may include both linear and branched alkyl groups. The alkyl group may have 1 to 7 carbon atoms, specifically 1 to 5, and specifically 1 to 4 carbon atoms. Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl; and examples of branched alkyl groups include, but are not limited to, isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylpentyl, 5-methylhexyl, 2,3-dimethylbutyl, 2,3-dimethylpentyl, and 2,4-dimethylpentyl.

[0032] The following provides a detailed description of this disclosure. However, this is illustrative only and the disclosure is not limited to the specific embodiments described herein.

[0033] One aspect of the present invention provides a trisilylamine compound that can be usefully used as a precursor for high-quality silicon thin films. Specifically, the trisilylamine compound according to one aspect may be represented by the following chemical formula 1.

[0034] [Chemical formula 1] [ka] (In the above chemical formula 1, R 1 ~R 7 These are, independently, hydrogen, C1-C7 alkyl, or fluoro.

[0035] The trisilylamine compound according to one embodiment has the structural characteristics described above, for example, a trisilylamine compound with a structure in which three silyl groups are substituted contains at least two silyl groups, each containing at least one fluoro(-F) group, which allows for the easy formation of high-purity silicon-containing thin films with a high deposition rate. Furthermore, the silicon-containing thin film produced from the trisilylamine compound according to one embodiment contains fluorine (F) and has an even lower dielectric constant, and is therefore expected to be useful as an insulating film material for semiconductor devices.

[0036] As an example, R 1 , R 4 , and R 6 These are, independently, hydrogen or fluoro, and R 2 , R 3 , R 5 , and R 7 Each of these may independently be hydrogen, a C1-C7 alkyl group, or a fluoro group, specifically hydrogen, a C1-C4 alkyl group, or a fluoro group, or hydrogen, a methyl group, or a fluoro group.

[0037] As an example, the trisilylamine compound may be represented by the following chemical formula 2.

[0038] [Chemical formula 2] [ka] (In the above chemical formula 2, R 1 ~R 3 and R 11 These are, independently, hydrogen, C1-C7 alkyl, or fluoro.

[0039] As an example, R 1 is hydrogen or fluoro, and R 2 and R 3 Each of these is independently hydrogen, C1-C7 alkyl, or fluoro, and R 11 This may be a C1-C7 alkyl or fluoro group.

[0040] As an example, R 2 and R 3 Each of these may independently be hydrogen, a C1-C4 alkyl group, or a fluoro group, specifically hydrogen, a C1-C4 alkyl group, or a fluoro group, and may be hydrogen, a methyl group, or a fluoro group.

[0041] As an example, R 11 This may be a C1-C4 alkyl or fluoro group, and may be methyl or fluoro group.

[0042] The aforementioned trisilylamine compound may be selected from, but is not limited to, the following structures. [ka]

[0043] The following describes in detail a method for producing the trisilylamine compound represented by chemical formula 1 according to one embodiment, but it goes without saying that it can also be synthesized by other methods that are easily recognizable to those skilled in the art. Furthermore, the organic solvent used is not limited, and the reaction time and temperature can also be changed within a range that does not deviate from the core of the invention.

[0044] A trisilylamine compound represented by chemical formula 1 according to one embodiment can be produced by (A) reacting a compound represented by the following chemical formula 21 with a chloride source to produce a compound represented by the following chemical formula 22, and (B) reacting a compound represented by the following chemical formula 22 with a fluoride source to produce a trisilylamine compound of chemical formula 1.

[0045] [Chemical formula 1] [ka]

[0046] [Chemical formula 21] [ka]

[0047] [Chemical formula 22] [ka] (In the above chemical formulas 1, 21, and 22, R 21 ~R 27 Each of these is independently hydrogen, C1-C7 alkyl, or NR a R b And, R 1 '~R 7 ' is independently hydrogen, C1-C7 alkyl, or chloro(Cl), R 1 ~R 7 These are, independently, hydrogen, C1-C7 alkyl, or fluoro(F), R a and R b Each of these is independently a C1-C7 alkyl group.

[0048] Step (A) is the -NR of the compound represented by chemical formula 21. a R bThe reaction involves substituting with -Cl, and may be carried out at 20-50°C for 1-10 hours, specifically at 20-30°C for 1-5 hours, but is not limited to this and can be modified depending on the reactants, the type and amount of solvent used.

[0049] The chloride source may be selected from, but is not limited to, hydrogen chloride (HCl), acetyl chloride (CH3COCl), thionyl chloride (SOCl2), silicon tetrachloride (SiCl4), and dichlorophenylphosphine (C6H5Cl2P).

[0050] Step (B) is a step of substituting -Cl with -F in the compound represented by chemical formula 22 using a fluoride source, the fluoride source may be selected from, but is not limited to, alkali metal fluorides such as LiF, KF, NaF, RbF, CsF, or transition metal fluorides such as AgF, AgF2, ZnF2, CuF2, CuF2·H2O, NiF2, SnF2, InF3, ScF3, TiF3, MnF3, CoF3, CrF3, AuF3, FeF3, MnF3, BiF3, SbF3.

[0051] The reaction in step (B) may be carried out at 20-50°C for 1-10 hours, specifically at 20-40°C for 1-8 hours, but is not limited to this and can be modified depending on the reactants, the type and amount of solvent used.

[0052] Furthermore, the trisilylamine compound represented by chemical formula 1 according to one embodiment can be produced by reacting the compound represented by the following chemical formula 31 with the compound represented by chemical formula 32.

[0053] [Chemical formula 1] [ka]

[0054] [Chemical formula 31] [ka]

[0055] [Chemical formula 32] [ka] (In the above chemical formulas 1, 31, and 32, R 1 ~R 7 These are, independently, hydrogen, C1-C7 alkyl, or fluoro.

[0056] The reaction between the compound represented by chemical formula 31 and the compound represented by chemical formula 32 may be carried out in the presence of a base catalyst selected from NaH, KH, n-BuLi, and LiH, and may be carried out at 20-50°C for 1-10 hours, specifically at 20-40°C for 1-8 hours, but is not limited thereto and can be modified depending on the reactants, the type and amount of solvent used.

[0057] The compound represented by chemical formula 31 can be produced by (a) reacting the compound represented by chemical formula 33 with the compounds of chemical formulas 34 and 35 to produce the compound represented by chemical formula 36, ​​and (b) reacting the compound represented by chemical formula 36 with a fluoride source to produce the compound represented by chemical formula 31.

[0058] [Chemical formula 31] [ka]

[0059] [Chemical formula 33] [ka]

[0060] [Chemical formula 34] [ka]

[0061] [Chemical formula 35] [ka]

[0062] [Chemical formula 36] [ka] (Among the above chemical formulas 31 and 33-36, R 4 '~R 7 ' is independently hydrogen, C1-C7 alkyl, or chloro(Cl), R 4 ~R 7 These are, independently, hydrogen, C1-C7 alkyl, or fluoro(F), R 31 ~R 36 Each of these is independently a C1-C7 alkyl group.

[0063] As an example, R 31 ~R 36 Each of these may independently be a C1-C7 alkyl group, a C1-C4 alkyl group, or a methyl group.

[0064] As an example, the compounds of chemical formulas 34 and 35 may be the same as R 31 ~R 36 These are identical to each other and may be C1-C7 alkyl, C1-C4 alkyl, or methyl.

[0065] Step (a) may be carried out at 50-200°C for 5-20 hours, specifically at 80-120°C for 5-10 hours, but this may be changed depending on the reactants, the type and amount of solvent used, and may be carried out until the by-products represented by the following chemical formulas 40 and 41 produced by the reaction are not recovered.

[0066] [Chemical formula 40] [ka]

[0067] [Chemical formula 41] [ka] (In the above chemical formulas 40 and 41, R 31 ~R 36 (This is as defined above.)

[0068] Step (b) is a step of substituting -Cl with -F in the compound represented by chemical formula 36 using a fluoride source, the fluoride source may be selected from, but is not limited to, alkali metal fluorides such as LiF, KF, NaF, RbF, CsF, or transition metal fluorides such as AgF, AgF2, ZnF2, CuF2, CuF2·H2O, NiF2, SnF2, InF3, ScF3, TiF3, MnF3, CoF3, CrF3, AuF3, FeF3, MnF3, BiF3, SbF3.

[0069] Step (b) may be carried out at 50-200°C for 1-10 hours, specifically at 50-100°C for 5-10 hours, but is not limited thereto and can be modified depending on the reactants, the type and amount of solvent used.

[0070] Furthermore, one aspect of the present invention provides a silicon-containing thin film deposition composition containing the trisilylamine compound. The silicon-containing thin film deposition composition according to one aspect (hereinafter referred to as the thin film deposition composition) always contains the trisilylamine compound represented by chemical formula 1 as a thin film deposition precursor, and the content of the compound represented by chemical formula 1 in the composition may be within a range that can be recognized by a person skilled in the art, taking into consideration the thin film deposition conditions or the thickness of the thin film, the characteristics of the thin film, the application of the thin film, etc.

[0071] Preferably, the silicon-containing thin film deposition composition according to one embodiment may be a fluorine and silicon-containing thin film deposition composition, and the thin film produced therefrom has a low dielectric constant and can be used as an insulating film material for semiconductor devices, and the thin film can also be used as a deposition suppression layer material, in which case the trisilylamine compound according to one embodiment can play the role of an inhibitor.

[0072] A further aspect of the present invention provides a method for producing a silicon-containing thin film, comprising the step of depositing a silicon-containing thin film using a trisilylamine compound represented by the following chemical formula 1, or a thin film deposition composition containing the same, and a reaction gas.

[0073] [Chemical formula 1] [ka] (In the above chemical formula 1, R 1 ~R 7 These are, independently, hydrogen, fluoro, or C1-C7 alkyl.

[0074] A method for producing a silicon-containing thin film according to one embodiment uses the trisilylamine compound represented by chemical formula 1 as a precursor, which allows for the production of a high-quality silicon-containing thin film with a high deposition rate, and preferably, a fluorine and silicon-containing thin film can be produced.

[0075] Specifically, the method for producing a silicon-containing thin film according to one embodiment has the advantage that the fluorine (F) of the trisilylamine compound represented by chemical formula 1 remains in the thin film, and a thin film containing both fluorine and silicon can be produced using a single precursor. In other words, generally, fluorine and silicon-containing thin films are produced by first producing a silicon-containing thin film and then doping it with fluorine using a fluorine-containing precursor. However, this method has the disadvantage that the fluorine content in the thin film may be non-uniform. In contrast, the method for producing a fluorine and silicon-containing thin film according to the present invention overcomes this disadvantage and makes it possible to produce a fluorine and silicon-containing thin film with a uniform fluorine content using a single precursor.

[0076] The aforementioned deposition method is not particularly limited as long as it is commonly used in the relevant field. For example, atomic layer deposition (ALD), chemical vapor deposition (CVD), metal-organic chemical vapor deposition (MOCVD), low-pressure chemical vapor deposition (LPCVD), plasma-enhanced chemical vapor deposition (PECVD), or plasma-enhanced atomic layer deposition (PEALD) can be used, but are not limited to these.

[0077] In a method for producing a silicon-containing thin film according to one embodiment, the trisilylamine compound and the reaction gas may be supplied continuously or discontinuously, and the discontinuous supply may include the form of a pulse.

[0078] As an example, the method for manufacturing the silicon-containing thin film may include: a) maintaining the temperature of a substrate mounted in a chamber at 100°C or higher; b) adsorbing a trisilylamine compound represented by chemical formula 1, or a thin film deposition composition containing the same, onto the substrate; and c) injecting a reaction gas onto the substrate on which the trisilylamine compound or thin film deposition composition is adsorbed, thereby depositing a silicon-containing thin film.

[0079] Specifically, the method for producing the silicon-containing thin film may include: a) maintaining the temperature of a substrate mounted in a chamber at 100°C or higher; b) adsorbing the trisilylamine compound represented by chemical formula 1, or a thin-film deposition composition containing the same, onto the substrate; c) purging the residual trisilylamine compound, or residual deposition composition and by-products; d) injecting a reaction gas into the substrate on which the trisilylamine compound, or thin-film deposition composition, is adsorbed to form a silicon-containing thin film; and e) purging the residual reaction gas and by-products.

[0080] The reaction gas is not particularly limited as long as it is commonly used in the art, but may be selected from oxygen (O2), ozone (O3), oxygen plasma, hydrogen (H2), hydrogen plasma, water (H2O), hydrogen peroxide (H2O2), nitrogen (NO2), nitric oxide (NO), nitrous oxide (N2O), ammonia (NH3), carbon dioxide (CO2), formic acid (HCOOH), acetic acid (CH3COOH), acetic anhydride ((CH3CO)2O), or a combination thereof.

[0081] Furthermore, the reaction gas may further contain a hydrocarbon gas, which may be a C2-C12 alkene, a C2-C10 alkene, or a C2-C6 alkene gas, and may be selected from, for example, 1-hexene, propylene, and acetylene. The hydrocarbon gas can be injected with an inert gas as a transfer gas.

[0082] The substrate is not particularly limited as long as it is commonly used in the field, but may be, for example, a substrate containing one or more semiconductor materials from among Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP, an SOI (Silicon On Insulator) substrate, a quartz substrate, a display glass substrate, or a flexible plastic substrate such as polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES), or polyester.

[0083] In addition to immediately forming a thin film on the substrate, the silicon-containing thin film may also be formed between the substrate and the silicon-containing thin film, with a number of conductive layers, dielectric layers, or insulating layers being further formed between them.

[0084] For example, the temperature of the substrate may be adjusted to 100-800°C, 300-800°C, or 400-700°C, but is not limited to these.

[0085] Furthermore, one aspect of the present invention provides a silicon-containing thin film produced by the above-described manufacturing method.

[0086] A silicon-containing thin film according to one embodiment may be any thin film that can be manufactured using the trisilylamine compound represented by chemical formula 1 as a precursor, as long as it is within the scope of what a person skilled in the art can recognize in the art. Specifically, this may include silicon oxide films, silicon nitride films, silicon carbonitride films, silicon carbide films, silicon fluoride carbide films, silicon fluoride oxide films, silicon fluoride films, silicon fluoride nitride films, and the like. In addition, various high-quality thin films containing silicon, or fluorine and silicon, can be manufactured, as long as it is within the scope of what a person skilled in the art can recognize.

[0087] The silicon-containing thin film not only exhibits excellent chemical and thermal stability but also has a very low dielectric constant, making it suitable for a variety of applications, such as insulating films, diffusion-blocking films, spacers, intermetallic dielectric materials, and protective film layers in the fabrication of electronic devices. Furthermore, the silicon-containing thin film according to one embodiment can be used as a deposition suppression layer, in which case the trisilylamine compound according to one embodiment can act as an inhibitor.

[0088] The above-mentioned implementation examples will be explained in more detail below with reference to embodiments. However, the embodiments below are for illustrative purposes only and do not limit the scope of rights.

[0089] <Synthesis of trisilylamine compounds> [Example 1] Synthesis of Bis(fluoromethylsilyl)methylsilylamine [ka] Under an anhydrous and inert atmosphere, a reflux apparatus was attached to a flame-dried 5 L flask. 800 g (3.40 mol) of bis((dimethyl)aminomethylsilyl)methylsilylamine and 2500 g (34.02 mol) of pentane were added, and after cooling to -30°C, 521 g (14.29 mol) of hydrogen chloride gas was slowly added while maintaining a temperature below -20°C. After the addition was complete, the temperature was gradually raised to room temperature and stirred for approximately 3 hours to complete the reaction. The reaction mixture was distilled under reduced pressure at 60°C and 14 torr to recover 520 g of bis(chloromethylsilyl)methylsilylamine (70% yield, 2.38 mol).

[0090] Under an anhydrous and inert atmosphere, 639 g (3.57 mol) of antimonite trifluoride (SbF3) and 678 g (4.76 mol) of decane (n-decane) were placed in a flame-dried 2 L flask. At room temperature, 520 g (2.38 mol) of bis(chloromethylsilyl)methylsilylamine prepared above was slowly added. The internal temperature was maintained below 35°C during the addition. After the addition was complete, the mixture was stirred for approximately 6 hours while maintaining a temperature below 35°C to complete the reaction. After filtering the reaction mixture, the filtrate was subjected to vacuum distillation at 35°C and 40 torr to obtain 309 g (1.67 mol) of the target compound, bis(fluoromethylsilyl)methylsilylamine (yield 70%, GC purity 99%). 1 H-NMR (C6D6): 0.10ppm (t, 3H, H2-Si-CH3), 0.14ppm (m, 6H, F-Si-CH3), 4.53ppm (m, 2H, CH3-Si-H2), 4.80~4.96ppm (dd, 2H, F-Si-H) 29 Si-NMR (CDCl3): -27.6ppm (d, Si, H2-Si), -8.4~-4.8ppm (dd, 2Si, Si-F)

[0091] [Example 2] Synthesis of Bis(fluoromethylsilyl)methylsilylamine [ka] A Dean-Stark reflux apparatus was attached to a flame-dried 2 L flask under an anhydrous and inert atmosphere. 300 g (1.86 mol) of hexamethyldisilazane and 855 g (3.26 mol) of dichloromethylsilane were added, and the mixture was heated at 80-120°C while recovering the resulting by-product, chlorotrimethylsilane, and any excess dichloromethylsilane. The mixture was heated and stirred for approximately 7-8 hours until no more chlorotrimethylsilane was produced or recovered. The reaction mixture was gradually cooled to room temperature, and then distilled under reduced pressure at 40°C and 0.5 torr to recover 291 g (90% yield, 1.67 mol) of 1,3-dichloro-1,3-dimethyldisilazane from the reaction mixture.

[0092] In a flame-dried 1 L flask under anhydrous and inert atmosphere, 449 g (2.51 mol) of SbF3 and 449 g (3.35 mol) of diethyleneglycoldimethyl ether (DEGDME) were placed, and 291 g (1.67 mol) of 1,3-dichloro-1,3-dimethyldisilazane prepared above was slowly added at room temperature. The internal temperature was maintained below 40°C during the addition. After the addition was complete, the mixture was stirred at 70°C for 8 hours and then filtered. The resulting filtrate was subjected to vacuum distillation at 45°C and 10 torr to recover 165 g (75% yield, 1.17 mol) of the target compound, 1,3-difluoro-1,3-dimethyldisilazane.

[0093] In a flame-dried 1 L flask under an anhydrous and inert atmosphere, 165 g (1.17 mol) of 1,3-difluoro-1,3-dimethyldisilazane prepared above and 606 g (7.03 mol) of hexane (n-hexane) were placed and cooled to -40 to -30°C. While maintaining the internal temperature below -30°C, a 2.5 M n-BuLi hexane solution was slowly added dropwise. While maintaining the internal temperature below -30°C, 94 g (1.17 mol) of chloromethylsilane was slowly added dropwise. The temperature was gradually raised to room temperature, stirred at room temperature for about 6 hours, and then filtered. The obtained filtrate was removed from the solvent hexane by simple distillation at 80-90°C and 760 torr, and then vacuum distillation was performed at 35°C and 40 torr to obtain 50 g (0.35 mol) of the target compound, bis(fluoromethylsilyl)methylsilylamine (yield 30%, GC purity 98%). 1 H-NMR (C6D6): 0.10ppm (t, 3H, H2-Si-CH3), 0.14ppm (m, 6H, F-Si-CH3), 4.53ppm (m, 2H, CH3-Si-H2), 4.80~4.96ppm (dd, 2H, F-Si-H) 29 Si-NMR (CDCl3): -27.6ppm (d, Si, H2-Si), -8.4~-4.8ppm (dd, 2Si, Si-F)

[0094] [Example 3] Synthesis of tri(fluoromethylsilyl)amine [ka] Under an anhydrous and inert atmosphere, a reflux apparatus was attached to a flame-dried 5 L flask. 500 g (1.79 mol) of tri((dimethyl)aminomethylsilyl)amine and 1295 g (17.95 mol) of pentane were added, and after cooling to -30°C, 275 g (7.54 mol) of hydrogen chloride gas was slowly added while maintaining the temperature below -20°C. After the addition was complete, the temperature was gradually raised to room temperature and stirred for approximately 3 hours to complete the reaction. 392 g (70% yield, 1.26 mol) of tri(chloromethylsilyl)amine was recovered from the reaction mixture under conditions of 65°C and 14 torr.

[0095] Under an anhydrous and inert atmosphere, 3337 g (1.88 mol) of SbF and 357 g (2.51 mol) of n-decane were placed in a flame-dried 2 L flask, and 392 g (1.26 mol) of tri(chloromethylsilyl)amine prepared above was slowly added at room temperature. The internal temperature was maintained below 35°C during the addition. After the addition was complete, the mixture was stirred for approximately 6 hours while maintaining a temperature below 35°C to complete the reaction. After filtering the reaction mixture, the filtrate was recovered at 35°C and 40 torr, and then distilled under reduced pressure to obtain 163 g (0.88 mol) of the target compound, tri(fluoromethylsilyl)amine (yield 70%, GC purity 98%). 1 H-NMR (C6D6): 0.15ppm (m, 9H, F-Si-CH3), 5.0ppm (m, 3H, F-Si-H) 29 Si-NMR (CDCl3): -6.5ppm (d, 2Si, Si-F)

[0096] Figure 1 shows the results of thermogravimetric analysis (TGA, L81-II, LINSEIS) and differential scanning calorimeter (DSC) analysis of bis(fluoromethylsilyl)methylsilylamine produced in Example 1.

[0097] Referring to Figure 1, it can be seen that the compound of Example 1 has a single evaporation step at approximately 100°C, exhibits very low residual mass and rapid vaporization characteristics, and is almost entirely vaporized without thermal decomposition. Furthermore, the DSC graph shows that the compound of Example 1 has excellent thermal stability.

[0098] <Thin film deposition> [Example 4] Thermal Atomic Layer Deposition (TALD) A silicon-containing thin film was manufactured using a conventional thermal atomic layer deposition (TALD) apparatus employing atomic layer deposition (ALD). Bis(fluoromethylsilyl)methylsilylamine, manufactured in Example 1, was used as the precursor, oxygen, hydrogen, and 1-hexene were used as the reaction gases, and argon was used as the purge gas.

[0099] The silicon substrate was set to a temperature of 630°C. As shown in Table 1 below, the precursor was packed into a stainless steel bubbler container and maintained at -1 to 24°C, and 1-hexene was packed into a stainless steel bubbler container and maintained at -20°C. First, the vaporized precursor in the stainless steel bubbler container was transferred to the silicon substrate for 1-20 seconds using 100 sccm of argon gas as the transfer gas, so that it would be adsorbed onto the silicon substrate. Secondly, 1,000-3,000 sccm of argon gas was used to remove unadsorbed precursors for approximately 10-20 seconds. Thirdly, 2,000 sccm of oxygen was used as the reaction gas for 10 seconds, or 1-hexene was used with 100 sccm of argon gas as the transfer gas for 20 seconds, followed by 2,000 sccm of oxygen for 10 seconds, or 500-2,000 sccm of oxygen and 100 sccm of hydrogen for 3 seconds, or 1-hexene was used with 100 sccm of argon gas as the transfer gas for 5-20 seconds, followed by 1,000-2,000 sccm of oxygen and 20-1,000 sccm of hydrogen for 1-3 seconds to form a thin film. Finally, 1,000-3,000 sccm of argon gas was used to remove reaction byproducts and residual reaction gases for approximately 10-20 seconds. The above process constituted one cycle, and a certain number of cycles were repeated to form a thin film.

[0100] Table 1 below shows the thin film deposition conditions. Detailed thin film deposition conditions, deposition results based on these conditions, the thickness of the deposited thin film, the refractive index (RI), and the density were measured and recorded in Table 2 below.

[0101] The thickness and refractive index (RI) of the deposited thin film were measured using an ellipsometer (OPTI-PROBE 2600, THERMA-WAVE).

[0102] [Table 1]

[0103] [Table 2]

[0104] Furthermore, the composition of the deposited thin film was analyzed using an X-ray photoelectron spectrometer, and the content values ​​of each atom in the deposited thin film, depending on the deposition conditions, are shown in Table 3 below. It was confirmed that by using the trisilylamine compound of the present invention as a precursor, a silicon oxide film can be deposited at a high deposition rate, a silicon oxide film containing fluorine can be formed, and other C and N compositions can be included by changing the thin film deposition conditions.

[0105] [Table 3]

[0106] [Example 5] 2-Step Thermal Atomic Layer Deposition (TALD) A silicon-containing thin film was manufactured using a conventional thermal atomic layer deposition (TALD) apparatus employing atomic layer deposition (ALD). Bis(fluoromethylsilyl)methylsilylamine, manufactured in Example 1, was used as the precursor, oxygen, hydrogen, and 1-hexene were used as the reaction gases, and argon was used as the purge gas.

[0107] The silicon substrate was set to a temperature of 630°C. As shown in Table 4 below, the precursor was packed into a stainless steel bubbler container and maintained at 9°C, and 1-hexene was packed into a stainless steel bubbler container and maintained at -20°C. First, the vaporized precursor in the stainless steel bubbler container was transferred to the silicon substrate for 1 second using 100 sccm of argon gas as the transfer gas to allow it to be adsorbed onto the silicon substrate. Second, 1,000 sccm of argon gas was used to remove any unadsorbed precursor for about 10 seconds. Third, 1-hexene was passed through as the reaction gas using 100 sccm of argon gas as the transfer gas for 10-40 seconds, and then 1,000 sccm of argon gas was used to remove any unadsorbed reactants for about 10 seconds. Fourth, 2000 sccm of oxygen and 1000 sccm of hydrogen were passed through as reaction gases for approximately 10-40 seconds to form a thin film, and 1000 sccm of argon gas was used to remove reaction byproducts and residual reaction gases for approximately 10 seconds. Finally, 1-hexene was passed through using 100 sccm of argon gas as the transfer gas for 10-40 seconds, and then 1000 sccm of argon gas was used to remove any unadsorbed reactants for approximately 10 seconds. The above process constituted one cycle, and a silicon oxide film was formed by repeating a certain number of cycles.

[0108] Table 4 below shows the thin film deposition conditions. Detailed deposition conditions, deposition results based on those conditions, the thickness of the deposited thin film, and the refractive index (RI) were measured and recorded in Table 5 below.

[0109] [Table 4]

[0110] [Table 5]

[0111] Furthermore, the composition of the deposited thin film was analyzed using an X-ray photoelectron spectrometer, and the content values ​​of each atom in the deposited thin film, depending on the deposition conditions, are shown in Table 6 below. It was found that by using the trisilylamine compound of the present invention as a precursor, a silicon oxide film can be deposited at a high deposition rate, and it was confirmed that the silicon oxide film contains fluorine.

[0112] [Table 6]

[0113] As described above, the present invention has been explained with specific details and limited examples and comparative examples, but these are provided only for a more general understanding of the invention, and the invention is not limited to the above examples. A person with ordinary skill in the art to which the invention belongs can make various modifications and variations from this description.

[0114] Therefore, the concept of the present invention should not be limited to the embodiments described above. Not only the claims attached, but also anything equivalent to these claims, or equivalent variations thereof, can all be said to fall within the scope of the concept of the present invention.

Claims

1. A trisilylamine compound represented by the following chemical formula 1. [Chemical formula 1] 【Chemistry 1】 (In the above chemical formula 1, R １ ~R ７ These are, independently, hydrogen, C1-C7 alkyl, or fluoro.

2. The aforementioned R １ , R ４ , and R ６ Each is independently hydrogen or fluoro, R ２ 、 R ３ 、 R ５ 、 and R ７ is, independently of one another, hydrogen, C1-C7 alkyl, or fluoro, the trisilylamine compound according to claim 1.

3. The trisilylamine compound according to claim 1, which is represented by the following chemical formula 2. [Chemical formula 2] 【Chemistry 2】 (In the above chemical formula 2, R １ ~R ３ and R １１ These are, independently, hydrogen, C1-C7 alkyl, or fluoro.

4. The aforementioned R １ is hydrogen or fluoro, R ２ and R ３ Each of these is independently hydrogen, C1-C7 alkyl, or fluoro. R １１ The trisilylamine compound according to claim 3, wherein is a C1-C7 alkyl or fluoro compound.

5. The trisilylamine compound according to claim 1, which is selected from the following structures. 【Transformation 3】

6. A silicon-containing thin film deposition composition comprising the trisilylamine compound described in any one of claims 1 to 5.

7. A silicon-containing thin film produced from a trisilylamine compound represented by the following chemical formula 1, or from a thin-film deposition composition containing the same. [Chemical formula 1] 【Chemistry 4】 (In the above chemical formula 1, R １ ~R ７ These are, independently, hydrogen, C1-C7 alkyl, or fluoro.

8. A method for producing a silicon-containing thin film, comprising using a trisilylamine compound represented by the following chemical formula 1, or a thin film deposition composition containing the same, and a reaction gas. [Chemical formula 1] 【Transformation 5】 (In the above chemical formula 1, R １ ~R ７ These are, independently, hydrogen, C1-C7 alkyl, or fluoro.

9. The reaction gas is oxygen (O ２ ), ozone (O ３ ), oxygen plasma, hydrogen (H ２ ), hydrogen plasma, water (H ２ O), hydrogen peroxide (H ２ O ２ ), nitrogen (NO ２ ), nitric oxide (NO), nitrous oxide (N ２ O), ammonia (NH ３ ), carbon dioxide (CO2) ２ ), formic acid (HCOOH), acetic acid (CH ３ COOH), acetic anhydride ((CH ３ CO) ２ A method for producing a silicon-containing thin film according to claim 8, comprising O), or a combination thereof.

10. The method for producing a silicon-containing thin film according to claim 9, wherein the reaction gas further comprises a hydrocarbon gas.

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