Fluoroaminosilane compound, method of producing the same, composition comprising the same and method for manufacturing a silicon-containing thin film

Abstract

A composition for depositing a silicon-containing thin film comprising a fluoroamine silane compound as a precursor is provided, as well as a method for manufacturing a silicon-containing thin film using the composition. The silicon-containing thin film manufactured therefrom has excellent chemical and thermal stability and a sufficiently low dielectric constant, and is therefore expected to be effectively used as an insulating film for semiconductor devices, particularly as an insulating film for spacers.

Description

[Technical Field]

[0001] This invention claims priority to Korean Patent Application No. 10-2024-0046416, filed with the Korean Intellectual Property Office on April 5, 2024, based on 35 U.SC §119, the disclosure of which is incorporated herein by reference in its entirety.

[0002] The following discloses a low-dielectric silicon-containing thin film, and more specifically, a composition comprising a novel fluoroamine silane compound for depositing a silicon-containing thin film and a silicon-containing thin film made therefrom. [Previous Technology]

[0003] Silicon-containing thin films manufactured by various deposition methods such as atomic layer deposition (ALD) and chemical vapor deposition (CVD) are used as semiconductor substrates, diffusion masks, antioxidant films, dielectric films, insulating films, etc. in semiconductor technology.

[0004] Meanwhile, for insulating films used as spacers in semiconductor devices, it is important to have low dielectric constant and excellent corrosion resistance. Furthermore, in order to apply them to actual processes, conditions such as ease of handling and excellent chemical and thermal stability should be met. Therefore, the physical properties required for insulating films suitable for spacers in next-generation semiconductor devices are gradually increasing.

[0005] Therefore, research on reducing the dielectric constant of silicon-containing thin films continues, but a sufficiently low dielectric constant cannot be guaranteed, or thermal stability and corrosion resistance are reduced, and productivity is reduced due to low film formation rate. Furthermore, as a method to simultaneously satisfy the requirements of low dielectric constant and corrosion resistance for silicon-containing thin films, a method of doping with fluorine (F) after the formation of the silicon-containing thin film has been proposed. However, this method further involves a fluorine doping step, which complicates the process. Doping mainly occurs near the surface of the film, making it difficult to perform F doping in regions deeper than the surface, and thus degrading the quality of the film.

[0006] [Prior Art Documents] [Patent Documents] Patent Document 1: Korean Patent Application Publication No. KR10-2012-0099926 (September 12, 2012). [Summary of the Invention]

[0007] Embodiments of the present invention aim to provide a composition for depositing silicon-containing thin films, which can provide high-quality low-dielectric thin films.

[0008] Another embodiment of the present invention aims to provide a manufacturing method that can deposit thin films at a high thin film deposition rate and manufacture high-quality silicon-containing thin films through a simple manufacturing process.

[0009] Yet another embodiment of the present invention aims to provide a fluoroaminosilane compound having a novel structure, which can be used as a precursor for depositing silicon-containing thin films; and to provide a method for manufacturing the fluoroaminosilane compound.

[0010] In a general embodiment, a composition for depositing silicon-containing thin films is provided, comprising a fluoroaminosilane compound represented by the following chemical formula 1: [Chemical Formula 1] wherein R1 is (C1-C7)alkyl; R2 is (C1-C7)alkyl or -Si(R11)(R12)(R13); R11 is fluoro; and R12 and R13 are independently hydrogen, (C1-C7)alkyl, fluoro or fluoro(C1-C7)alkyl.

[0011] R1 may be a branched (C3-C7) alkyl; R2 may be a branched (C3-C7) alkyl or -Si(R11)(R12)(R13); R11 may be fluorinated; and R12 and R13 may be hydrogen or (C1-C4) alkyl independently of each other.

[0012] Fluoroaminosilane compounds may be selected from the following compounds:

[0013] In another general embodiment, a method for manufacturing a silicon-containing thin film is provided, which uses a fluoroaminosilane compound represented by the following chemical formula 1 or a composition comprising the aforementioned compound for depositing a silicon-containing thin film: [Chemical Formula 1] wherein R1 is (C1-C7)alkyl; R2 is (C1-C7)alkyl or -Si(R11)(R12)(R13); R11 is fluoro; and R12 and R13 are independently hydrogen, (C1-C7)alkyl, fluoro or fluoro(C1-C7)alkyl.

[0014] The method for manufacturing a silicon-containing thin film according to an embodiment may include: step a) maintaining the temperature of a substrate mounted in a chamber at 100°C or higher; step b) contacting a fluoroamine silane compound represented by chemical formula 1 or the composition for depositing a silicon-containing thin film including the compound with the substrate to adsorb it onto the substrate; and step c) injecting a reactive gas into the substrate on which the fluoroamine silane compound or the composition for depositing a silicon-containing thin film has been adsorbed to form a silicon-containing thin film.

[0015] The manufacturing method can be performed by 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).

[0016] The silicon-containing thin film according to the embodiment may further contain fluorine.

[0017] In another general example, a fluoroaminosilane compound represented by the following chemical formula 1 is provided: [Chemical Formula 1] wherein R1 is (C1-C7)alkyl; R2 is (C1-C7)alkyl or -Si(R11)(R12)(R13); R11 is fluoro; and R12 and R13 are independently hydrogen, (C1-C7)alkyl, fluoro or fluoro(C1-C7)alkyl.

[0018] In yet another general example, a method for producing a fluoroaminosilane compound includes: reacting a compound represented by the following chemical formula 11 with a compound represented by the following chemical formula 12 to prepare a compound represented by the following chemical formula 13; and reacting the compound represented by chemical formula 13 with a fluoride source to produce a fluoroaminosilane compound represented by chemical formula 1: [Chemical Formula 1][Chemical Formula 11][Chemical Formula 12][Chemical Formula 13] wherein, X is hydrogen or Cl; R1 is (C1-C7)alkyl; R2 is (C1-C7)alkyl or -Si(R11)(R12)(R13); R11 is fluoro; and R12 and R13 are independently hydrogen, (C1-C7)alkyl, fluoro or fluoro(C1-C7)alkyl.

[0019] The fluoride source may be selected from the group consisting of: LiF, KF, NaF, RbF, CsF, AsF 3, AsF 5, AgF, AgF 2, ZnF 2, CuF 2, CuF 2·H 2O, NiF 2, SnF 2, InF 3, ScF 3, TiF 3, MnF 3, CoF 3, CrF 3, AuF 3, FeF 3, MnF 3, BiF 3, SbF 3, SbF 5, and NaBF 4.

[0020] Other features and features will become apparent from the following detailed description, drawings and claims.

Implementation Method

[0023] In this specification, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein is for the purpose of effectively describing a particular instance and is not intended to limit the invention.

[0024] Unless otherwise stated in the context, the singular form used in this invention may also include the plural form.

[0025] In addition, the numerical range used in this specification includes all values ​​within the range including the lower and upper limits, increments derived in the form and span logic of the defined range, all double limits, and all possible combinations of the upper and lower limits of the numerical range defined in different forms. Unless otherwise defined in this specification, values ​​that may be outside the numerical range due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0026] The term "comprising" as described in this specification is an open-ended description and has the same meaning as terms such as "provided", "containing", "having" or "characterized in", and does not exclude elements, materials or processes not further listed.

[0027] The term "alkyl" as used in this specification is an organic radical derived from an aliphatic hydrocarbon by removing a hydrogen atom, and may include both straight-chain and branched-chain alkyl groups. An alkyl group may have 1 to 7, specifically 1 to 5, and more specifically 1 to 4 carbon atoms. As examples, straight-chain alkyl groups may include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl, and branched-chain alkyl groups may include isopropyl, secondary butyl, isobutyl, tertiary 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-methylhexyl, 5-methylhexyl, 2,3-dimethylbutyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, etc., but are not limited thereto.

[0028] In this specification, the term "alkenyl" refers to a straight-chain or branched unsaturated hydrocarbon radical containing one or more double bonds, and "alkynyl" refers to a straight-chain or branched unsaturated hydrocarbon radical containing one or more triple bonds.

[0029] The present invention will be described in detail below.

[0030] The composition for depositing silicon-containing thin films according to embodiments of the present invention may include precursor compounds having a specific structure to provide high-quality low-dielectric silicon-containing thin films.

[0031] Specifically, the precursor compound according to the embodiments can be a fluoroaminosilane compound represented by the following chemical formula 1: [Chemical Formula 1] wherein R1 is (C1-C7)alkyl; R2 is (C1-C7)alkyl or -Si(R11)(R12)(R13); R11 is fluoro; and R12 and R13 are independently hydrogen, (C1-C7)alkyl, fluoro or fluoro(C1-C7)alkyl.

[0032] Because the fluoroaminosilane compound represented by Formula 1 has the structural features described above, for example, simultaneously possessing Si-N and Si-F bonds, high-purity silicon-containing thin films can be easily formed at high deposition rates, and the silicon-containing thin film can further contain fluorine (F) and achieve a low dielectric constant. Preferably, the composition for depositing silicon-containing thin films according to the embodiments can be a composition for depositing fluorine-containing and silicon thin films, and the thin film manufactured therefrom has a low dielectric constant and can be used as an insulating material for semiconductor devices. Furthermore, the thin film can also serve as a deposition inhibition layer material, wherein a fluoroaminosilane compound of one state can act as an inhibitor.

[0033] As an example, R1 may be (C1-C4)alkyl; R2 may be (C1-C4)alkyl or -Si(R11)(R12)(R13); R11 may be fluorinated; and R12 and R13 may be hydrogen, (C1-C4)alkyl, fluorinated or fluorinated (C1-C4)alkyl independently of each other.

[0034] As an example, R1 may be a branched (C3-C7) alkyl; R2 may be a branched (C3-C7) alkyl or -Si(R11)(R12)(R13); R11 may be fluorinated; and R12 and R13 may be hydrogen or (C1-C4) alkyl independently of each other.

[0035] As an example, R1 may be a branched (C3-C5) alkyl; R2 may be a branched (C3-C5) alkyl or -Si(R11)(R12)(R13); R11 may be fluorinated; and R12 and R13 may be hydrogen or (C1-C3) alkyl independently of each other.

[0036] As an example, R1 and R2 can be the same and can be branched (C3-C7) alkyl groups, more specifically, R1 and R2 can be the same and can be branched (C3-C5) alkyl groups.

[0037] The fluoroaminosilane compound according to the embodiments may be selected from the following compounds, but is not limited thereto:

[0038] The composition for depositing silicon-containing thin films according to the embodiments must include a fluoroaminosilane compound represented by chemical formula 1 as a precursor for depositing the thin film, and the content of the compound represented by chemical formula 1 in the composition can be within the range that can be recognized by those skilled in the art to which this application pertains, taking into account the film formation conditions, film thickness, film properties, and film application.

[0039] In addition, embodiments of the present invention provide a method for manufacturing a silicon-containing thin film using a fluoroaminosilane compound represented by the following chemical formula 1 or a composition containing the compound for depositing a silicon-containing thin film.

[0040] [Chemical Formula 1] wherein R1 is (C1-C7)alkyl; R2 is (C1-C7)alkyl or -Si(R11)(R12)(R13); R11 is fluorinated; and R12 and R13 are independently hydrogen, (C1-C7)alkyl, fluorinated or fluorinated (C1-C7)alkyl.

[0041] Since the method for manufacturing silicon-containing thin films according to the embodiments uses a composition comprising a fluoroaminosilane compound represented by chemical formula 1 as a precursor, high-quality silicon-containing thin films can be manufactured at a high deposition rate, and preferably, thin films containing fluorine and silicon can be manufactured.

[0042] Specifically, since the fluorine (F) of the fluoroaminosilane compound represented by chemical formula 1 is retained in the film, the method for manufacturing silicon-containing films according to the embodiments can provide high-quality fluorine-containing and silicon-containing films.

[0043] The silicon-containing thin film according to the embodiments can be any thin film that can be manufactured within the scope of those skilled in the art to which this invention pertains, and specifically, it can be a silicon oxide (SiO2) film, a silicon nitride (SiN) film, a silicon carbonitride (SiCN) film, a silicon carbide (SiC) film, a fluorine silicon oxide (SiOF) film, a fluorine silicon carbide (SiCF) film, a fluorine silicon carbonitride (SiCNF) film, a fluorine silicon oxynitride (SiONF) film, etc. In addition, various high-quality thin films containing silicon or fluorine and silicon can be manufactured within the scope of those skilled in the art to which this invention pertains.

[0044] The silicon-containing thin films according to the embodiments exhibit excellent chemical and thermal stability, making them suitable for a variety of applications, such as use as insulating layers, diffusion barrier layers, spacers, intermetallic dielectric materials, or protective layers in the manufacture of electronic devices. Furthermore, the silicon-containing thin films according to the embodiments can be used as deposition inhibition layers, wherein a fluoroaminosilane compound of one state can act as an inhibitor.

[0045] The deposition method of the thin film in the method for manufacturing silicon-containing thin films according to the embodiments is not particularly limited, as long as it is commonly used in the art. However, 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. In particular, atomic layer deposition (ALD) or plasma-enhanced atomic layer deposition (PEALD) can be used, but the present invention is not limited thereto.

[0046] Specifically, the method for manufacturing a silicon-containing thin film according to the embodiments may include: step a) maintaining the temperature of a substrate mounted in a chamber at 100°C or higher; step b) contacting the composition for depositing a silicon-containing thin film according to the embodiments of the present invention with the substrate to adsorb the composition onto the substrate; and step c) injecting a reactive gas into the substrate on which the composition for depositing a silicon-containing thin film is adsorbed to form a silicon-containing thin film.

[0047] More specifically, the method for manufacturing a silicon-containing thin film may include: step a) maintaining the temperature of a substrate mounted in a chamber at 100°C or higher; step b) contacting the composition for depositing a silicon-containing thin film according to an embodiment of the invention with the substrate to adsorb the composition onto the substrate; step c) purging residual composition and byproducts used for deposition; step d) injecting a reactive gas into the substrate on which the composition for depositing a silicon-containing thin film is adsorbed to form a silicon-containing thin film; and step e) purging residual reactive gas and byproducts.

[0048] Although there are no particular limitations on the substrate, it can be any material commonly used in the art, such as a substrate containing one or more semiconductor materials selected from Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs and InP; silicon insulator (SOI) substrate; quartz substrate; or glass substrate for display; or flexible plastic substrate, such as polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyether ether (PES) and polyester (PE).

[0049] In addition, silicon-containing thin films can be formed directly on the substrate, and multiple conductive layers, dielectric layers, insulating layers, etc. can be further formed between the substrate and the silicon-containing thin film.

[0050] As an example, the temperature of the substrate may be specifically 100°C to 800°C, 300°C to 800°C, or 400°C to 700°C, and under said temperature conditions, the fluorine (F) of the fluoroamine silane compound represented by chemical formula 1 can be retained in the film, providing high-quality fluorine-containing and silicon films, and providing films with a low dielectric constant.

[0051] As an example, the reaction gas can be supplied after plasma activation reaction gas is generated at 50W to 1,000W, 100W to 800W or 400W to 600W.

[0052] The type of reactant gas is not particularly limited, as long as it is commonly used in the art. However, as examples, it may be oxygen (O2), ozone (O3), oxygen plasma, hydrogen (H2), hydrogen plasma, water (H2O), hydrogen peroxide (H2O2), nitrogen dioxide (NO2), nitric oxide (NO), nitrous oxide (N2O), ammonia (NH3), carbon dioxide (CO2), formic acid (HCOOH), acetic acid (CH3COOH), anhydrous acetic acid ((CH3CO)2O), or combinations thereof. The purging gas may be nitrogen (N2), argon (Ar), helium (He), or combinations thereof.

[0053] In the method for manufacturing a silicon-containing thin film according to the embodiment, the deposition conditions can be adjusted according to the desired structure or thermal properties of the thin film. The deposition conditions according to the embodiment may be, for example, the input flow rate of the composition for depositing the silicon-containing thin film, including the compound of Formula 1, the input flow rate of the reactant gas, the input flow rate of the carrier gas, the pressure, the RF power, the substrate temperature, etc. As a non-limiting example, the input flow rate of the composition for depositing the silicon-containing thin film may be 10 to 1000 cc / min, the input flow rate of the carrier gas may be 10 to 1000 cc / min, the flow rate of the reactant gas may be 1 to 3000 cc / min, the pressure may be 0.5 to 10 Torr, and the RF power and substrate temperature may be as described above.

[0054] In addition, another embodiment of the present invention provides a novel compound that can be used as a precursor for silicon-containing thin films. Specifically, the novel compound may be a fluoroaminosilane compound represented by the following chemical formula 1: [Chemical Formula 1] wherein R1 is (C1-C7)alkyl; R2 is (C1-C7)alkyl or -Si(R11)(R12)(R13); R11 is fluoro; and R12 and R13 are independently hydrogen, (C1-C7)alkyl, fluoro, or fluoro(C1-C7)alkyl.

[0055] Since the fluoroaminosilane compound represented by Chemical Formula 1 has the structural features described above, for example, having both Si-N bonds and Si-F bonds, high-purity silicon-containing thin films can be easily formed at a high deposition rate. Furthermore, since the thin film manufactured from the composition for depositing silicon-containing thin films according to the embodiments has a low dielectric constant, the thin film can be used as an insulating material for semiconductor devices.

[0056] As an example, R1 may be (C1-C4)alkyl; R2 may be (C1-C4)alkyl or -Si(R11)(R12)(R13); R11 may be fluorinated; and R12 and R13 may be hydrogen, (C1-C4)alkyl, fluorinated or fluorinated (C1-C4)alkyl independently of each other.

[0057] As an example, R1 may be a branched (C3-C7) alkyl; R2 may be a branched (C3-C7) alkyl or -Si(R11)(R12)(R13); R11 may be fluorinated; and R12 and R13 may be hydrogen or (C1-C4) alkyl independently of each other.

[0058] As an example, R1 may be a branched (C3-C5) alkyl; R2 may be a branched (C3-C5) alkyl or -Si(R11)(R12)(R13); R11 may be fluorinated; and R12 and R13 may be hydrogen or (C1-C3) alkyl independently of each other.

[0059] As an example, R1 and R2 can be the same and can be branched (C3-C7) alkyl groups, more specifically, R1 and R2 can be the same and can be (C3-C5) alkyl groups.

[0060] The fluoroaminosilane compound according to the embodiments may be selected from the following compounds, but is not limited thereto:

[0061] The method for manufacturing the fluoroaminosilane compound represented by chemical formula 1 will be described in detail below. However, the compound can also be synthesized by methods recognized by those skilled in the art to which this invention pertains. Of course, the organic solvents used herein are not limited, and of course, the reaction time and temperature can be changed without departing from the spirit of the invention.

[0062] A method for manufacturing a fluoroaminosilane compound according to an embodiment may include: (A) reacting a compound represented by the following chemical formula 11 with a compound represented by the following chemical formula 12 to produce a compound represented by the following chemical formula 13; and (B) reacting a compound represented by the following chemical formula 13 with a fluoride source to produce a fluoroaminosilane compound represented by chemical formula 1: [Chemical Formula 1][Chemical Formula 11][Chemical Formula 12][Chemical Formula 13] wherein, X is hydrogen or Cl; R1 is (C1-C7)alkyl; R2 is (C1-C7)alkyl or -Si(R11)(R12)(R13); R11 is fluoro; and R12 and R13 are independently hydrogen, (C1-C7)alkyl, fluoro or fluoro(C1-C7)alkyl.

[0063] (A) It can be carried out for 1 to 10 hours at 0°C to 30°C, specifically, for 1 to 5 hours at 10°C to 30°C, but not limited thereto, and can be varied depending on the type and amount of the reaction material and solvent used.

[0064] The fluoride source may be selected from the group consisting of: LiF, KF, NaF, RbF, CsF, AsF3, AsF₅, AgF, AgF2, ZnF₂, CuF2, CuF2·H2O, NiF2, SnF2, InF3, ScF3, TiF3, MnF3, CoF3, CrF3, AuF3, FeF3, MnF3, BiF3, SbF3, SbF₅, and NaBF4, etc. However, it is not limited to these examples and may include any fluorinating agent commonly used in the relevant art without limitation.

[0065] In addition, (B) can be carried out at 0°C to 30°C for 1 to 10 hours, specifically at 10°C to 30°C for 1 to 5 hours, but not limited thereto, and can be changed depending on the type and amount of the reaction material and solvent used.

[0066] The above-described embodiments will be described in detail below through the following examples. However, the following examples are for illustration only and do not limit the scope of the claims.

[0067] [Example 1] Synthesis of trifluoro(diisopropyl)aminosilane

[0068] Under an anhydrous and inert atmosphere, 514.0 g (3.03 mol) of tetrachlorosilane and 3710.0 g (51.43 mol) of pentane were added to a flame-dried 10 L flask. Diisopropylamine (673.5 g, 6.66 mol) was slowly added, and the mixture was stirred at room temperature for 5 hours. After the reaction was complete, the diisopropylamine hydrochloride was removed by filtration, and the solvent was removed at 60 °C and 6 Torr to give 638.9 g of trichloro(diisopropyl)aminosilane in 90.0% yield.

[0069] Under an anhydrous inert atmosphere, 636.5 g (2.71 mol) of the previously prepared trichloro(diisopropyl)aminosilane and 1194.0 g (8.90 mol) of diethylene glycol dimethyl ether were added to a flame-dried 3L flask and stirred. While maintaining the internal reaction temperature at 20-50 °C, 727.4 g (4.07 mol) of antimony(III) fluoride was added. The solvent was removed at 30 °C and 26 Torr, and the product was purified at 110 °C and 760 Torr to give 261.3 g of trifluoro(diisopropyl)aminosilane in a yield of 52.0%.

[0070] 1H-NMR (C 6D 6): 0.98ppm (d, 12H, N-(CH-(CH 3) 2) 2), 2.96ppm (m, 2H, N-(CH-(CH 3) 2) 2).

[0071] 13C-NMR (C 6D 6): 46.62ppm (s, 2C, N-(CH-(CH 3) 2) 2), 23.44ppm (s, 4C, N-(CH-(CH 3) 2) 2).

[0072] 29Si-NMR (C 6D 6): -83.22ppm (q, 1Si).

[0073] [Example 2] Synthesis of trifluoro(diisopropyl)aminosilane

[0074] Under an anhydrous and inert atmosphere, 427.0 g (3.15 mol) of trichlorosilane and 3866.6 g (53.59 mol) of pentane were added to a flame-dried 10 L flask. Diisopropylamine (701.8 g, 6.94 mol) was slowly added at room temperature, and the mixture was stirred at ambient temperature for 5 hours. After the reaction was complete, the diisopropylamine hydrochloride was removed by filtration, and the solvent was removed at 60 °C and 10 Torr to give 568.0 g of dichloro(diisopropyl)aminosilane in 90.0% yield.

[0075] Under an anhydrous and inert atmosphere, 567.0 g (2.83 mol) of the previously prepared dichloro(diisopropyl)aminosilane and 912.0 g (6.80 mol) of diethylene glycol dimethyl ether were added to a flame-dried 3 L flask and stirred. The reaction temperature was maintained at 20–50 °C, and 759.5 g (4.25 mol) of antimony(III) fluoride was added. The solvent was removed at 30 °C and 26 Torr, and the product was purified at 110 °C and 760 Torr to give 135.0 g of trifluoro(diisopropyl)aminosilane in a yield of 25.7%.

[0076] 1H-NMR (C 6D 6): 0.98ppm (d, 12H, N-(CH-(CH 3) 2) 2), 2.96ppm (m, 2H, N-(CH-(CH 3) 2) 2).

[0077] 13C-NMR (C 6D 6): 46.62ppm (s, 2C, N-(CH-(CH 3) 2) 2), 23.44ppm (s, 4C, N-(CH-(CH 3) 2) 2).

[0078] 29Si-NMR (C 6D 6): -83.22ppm (q, 1Si)

[0079] Figure 1 shows the results of thermogravimetric analysis (TGA, L81-II, LINSEIS) and differential scanning calorimetry (DSC) analysis of the fluoroaminosilane prepared in Example 1. Referring to Figure 1, it was found that the compound of Example 1 exhibited a single evaporation step at approximately 100°C, with very low residue mass, thus demonstrating rapid evaporation characteristics, and almost all of the compound evaporated without thermal decomposition. This indicates that the use of the fluoroaminosilane compound of the present invention is beneficial for the deposition of silicon-containing thin films.

[0080] Figure 2 shows the vapor pressure measurement of the fluoroaminosilane compound prepared in Example 1. Referring to Figure 2, it can be observed that the fluoroaminosilane compound of the present invention can be effectively used as a precursor for depositing silicon-containing thin films. This indicates that using this compound is beneficial for the deposition of silicon-containing thin films.

[0081] The composition for depositing silicon-containing thin films according to embodiments of the present invention is easy to store and dispose of, allows for the deposition of thin films at high film deposition rates, and can produce high-purity, low-dielectric silicon-containing thin films with high quality through a simple manufacturing process.

[0082] In addition, the silicon-containing thin film according to the embodiment has both excellent chemical and thermal stability and a sufficiently low dielectric constant, and therefore is expected to be effectively used as an insulating film for semiconductor devices, especially as a spacer in semiconductor miniaturization processes.

[0083] Although the present invention has been described above with reference to specific examples, instances, and comparative examples, these are only for the purpose of helping to understand the invention as a whole. Therefore, the present invention is not limited to the above examples. Those skilled in the art to which this invention pertains can make various modifications and variations based on this description.

[0084] Therefore, the spirit of the present invention should not be limited to the exemplary embodiments described above, and the following claims and all modifications that are equal to or equivalent to the claims are intended to fall within the scope and spirit of the present invention. [Simplified Explanation of the Diagram]

[0021] Figure 1 shows the TGA and DSC analysis results of the trifluoro(diisopropyl)aminosilane compound prepared in Example 1.

[0022] Figure 2 is a vapor pressure curve of the trifluoro(diisopropyl)aminosilane compound manufactured in Example 1.

Claims

1. A composition for depositing silicon-containing thin films, comprising a fluoroaminosilane compound represented by the following chemical formula 1: [Chemical Formula 1] wherein, R1 is a branched (C3-C7) alkyl group; R2 is a branched (C3-C7) alkyl group or -Si(R11)(R12)(R13); R11 is a fluorinated group; and R12 and R13 are independently hydrogen, (C1-C7) alkyl, fluorinated or fluorinated (C1-C7) alkyl.

2. The composition for depositing silicon-containing thin films as described in claim 1, wherein, R12 and R13 are independently hydrogen or (C1-C4) alkyl groups.

3. The composition for depositing silicon-containing thin films as described in claim 1, wherein, The aforementioned fluoroaminosilane compounds are selected from the following compounds: .

4. A method for manufacturing a silicon-containing thin film, the method using a fluoroaminosilane compound represented by the following chemical formula 1 or a composition comprising the aforementioned compound for depositing a silicon-containing thin film: [Chemical Formula 1] wherein, R1 is (C1-C7)alkyl; R2 is (C1-C7)alkyl or -Si(R11)(R12)(R13); R11 is fluoro; and R12 and R13 are independently hydrogen, (C1-C7)alkyl, fluoro or fluoro(C1-C7)alkyl.

5. The method for manufacturing a silicon-containing thin film as described in claim 4, wherein, The aforementioned method includes the following steps: step a) maintaining the temperature of a substrate mounted in a chamber at 100°C or higher; step b) contacting the aforementioned fluoroamine silane compound represented by chemical formula 1 or the aforementioned composition for depositing a silicon-containing thin film comprising the aforementioned compound with the aforementioned substrate to adsorb it onto the aforementioned substrate; and step c) injecting a reaction gas into the aforementioned substrate on which the aforementioned fluoroamine silane compound or the aforementioned composition for depositing a silicon-containing thin film has been adsorbed to form a silicon-containing thin film.

6. The method for manufacturing a silicon-containing thin film as described in claim 4, wherein, The aforementioned methods are performed by 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).

7. The method for manufacturing a silicon-containing thin film as described in claim 4, wherein, The aforementioned silicon-containing thin film further contains fluorine.

8. A fluoroaminosilane compound represented by the following chemical formula 1, [Chemical Formula 1] wherein, R1 is a branched (C3-C7) alkyl group; R2 is a branched (C3-C7) alkyl group or -Si(R11)(R12)(R13); R11 is a fluorinated group; and R12 and R13 are independently hydrogen, (C1-C7) alkyl, fluorinated or fluorinated (C1-C7) alkyl.

9. A method for manufacturing a fluoroaminosilane compound, the method comprising the steps of: reacting a compound represented by chemical formula 11 with a compound represented by chemical formula 12 to prepare a compound represented by chemical formula 13; and reacting the aforementioned compound represented by chemical formula 13 with a fluoride source to manufacture a fluoroaminosilane compound represented by chemical formula 1: [Chemical Formula 1] [Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13] wherein, X is hydrogen or Cl; R1 is (C1-C7)alkyl; R2 is (C1-C7)alkyl or -Si(R11)(R12)(R13); R11 is fluorinated; and R12 and R13 are independently hydrogen, (C1-C7)alkyl, fluorinated or fluorinated (C1-C7)alkyl.

10. The method for manufacturing a fluoroaminosilane compound as described in claim 9, wherein, The aforementioned fluoride sources are selected from the group consisting of: LiF, KF, NaF, RbF, CsF, AsF3, AsF5, AgF, AgF2, ZnF2, CuF2, CuF2·H2O, NiF2, SnF2, InF3, ScF3, TiF3, MnF3, CoF3, CrF3, AuF3, FeF3, MnF3, BiF3, SbF3, SbF5, and NaBF4.

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