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

Abstract

The present invention relates to a fluorodisilazane compound, a silicon-containing thin film deposition composition containing the same, and a method for producing a silicon-containing thin film using the same. The silicon-containing thin film produced from the fluorodisilazane compound according to the present invention not only has excellent chemical and thermal stability but also a low dielectric constant, making it usefully applicable as an insulating film for semiconductor devices, particularly as a spacer in semiconductor miniaturization processes.

Description

Technical Field

[0001] The present invention relates to a fluorodisilazane compound used as a precursor for a silicon-containing thin film, a composition for depositing a silicon-containing thin film containing the same, and a method for producing a silicon-containing thin film using the same.

Background Art

[0002] Silicon-containing thin films produced 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, and insulating films in semiconductor technology.

[0003] On the other hand, it is extremely important for the insulating film for the spacer of a semiconductor element to have a low dielectric constant and excellent etching resistance. Further, in order to be applied to an actual process, it must satisfy conditions such as ease of process, excellent chemical and thermal stability, etc. Therefore, the required physical properties of the insulating film for the spacer applied to next-generation semiconductor elements are gradually becoming more sophisticated.

[0004] For this reason, research has been continued to lower the dielectric constant of the silicon-containing thin film, but there are problems that a sufficiently low dielectric constant cannot be ensured, or the thermal stability and etching resistance are lowered, and the productivity is lowered due to a low thin film formation rate. Also, as a method for simultaneously satisfying the low dielectric constant and etching resistance of the silicon-containing thin film, a method of doping fluorine (F) after forming the silicon-containing thin film has been proposed. However, this is accompanied by an additional fluorine doping step, so the process becomes complicated, and doping is mainly performed only near the surface of the thin film, and it is difficult to perform F doping in a region deeper than the surface, so there is a limit in that the quality of the thin film is lowered.

Summary of the Invention

Problems to be Solved by the Invention

[0005] One aspect of the present invention provides a fluorodisilazane compound used as a precursor for high-quality silicon-containing thin films, and a silicon-containing thin film deposition composition containing the same.

[0006] Furthermore, one aspect of the present invention provides a method for manufacturing a silicon-containing thin film that enables the deposition of a thin film with a high thin-film deposition rate even under mild conditions, and that allows for the production of high-quality thin films in high yield. [Means for solving the problem]

[0007] One aspect of the present invention provides a fluorodisilazane compound represented by the following chemical formula 1.

[0008] [ka]

[0009] (In the above chemical formula 1,

number

number

number

[0010] The fluorodisilazane compound according to one embodiment may be represented by the following Chemical Formula 2 or 3.

[0011]

Chemical formula

[0012]

Chemical formula

[0013] (In the Chemical Formulas 2 and 3, A1 and A2 are each independently a single bond or (C1-C4)alkylene, R1 is hydrogen, (C1-C4)alkyl, (C2-C4)alkenyl, or (C2-C4)alkynyl, R2 and R3 are each independently hydrogen, fluoro, cyano, isocyanate, (C1-C4)alkyl, fluoro(C1-C4)alkyl, (C2-C4)alkenyl, fluoro(C2-C4)alkenyl, fluoro(C2-C4)alkynyl, or (C2-C4)alkynyl, R4 to R9 are each independently hydrogen, fluoro, fluoro(C1-C4)alkyl, or (C1-C4)alkyl.)

[0014] The fluorodisilazane compound according to one embodiment may be represented by the following Chemical Formula 4 or 5.

[0015]

Chemical formula

[0016] [Chemical formula]

[0017] (In the above chemical formulas 2 and 3, A1 and A2 are each independently a single bond or (C1-C4) alkylene, R1 is hydrogen, (C1-C4) alkyl, (C2-C4) alkenyl, or (C2-C4) alkynyl, R2 and R3 are each independently hydrogen, fluoro, cyano, isocyanate, (C1-C4) alkyl, fluoro (C1-C4) alkyl, (C2-C4) alkenyl, fluoro (C2-C4) alkenyl, fluoro (C2-C4) alkynyl, or (C2-C4) alkynyl, R4 to R9 are each independently hydrogen, fluoro, fluoro (C1-C4) alkyl, or (C1-C4) alkyl.)

[0018] The fluorodisilazane compound according to one aspect may be represented by the following chemical formula 4 or 5.

[0019] [Chemical formula]

[0020] [Chemical formula]

[0021] (In the above chemical formulas 4 and 5, R1 is hydrogen, (C1-C4) alkyl, or (C2-C4) alkenyl, R2 and R3 are, independently, hydrogen, fluoro, cyano, isocyanate, (C1-C4) alkyl, fluoro(C1-C4) alkyl, fluoro(C2-C4) alkenyl, or (C2-C4) alkenyl.

[0022] The fluorodisilazane compound according to one embodiment may be selected from the following compounds. [ka]

[0023] Another aspect of the present invention provides a silicon-containing thin film deposition composition comprising the fluorodisilazane compound.

[0024] Another 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 fluorodisilazane compound represented by the following chemical formula 1, or a silicon-containing thin film deposition composition containing the same.

[0025] [ka]

[0026] (In the above chemical formula 1,

number

[0027] A method for manufacturing the silicon-containing thin film according to one embodiment may include the steps of: maintaining the temperature of a substrate mounted in a chamber at 100°C or higher; adsorbing a fluorodisilazane compound represented by chemical formula 1, or a silicon-containing thin film deposition composition, onto the substrate; and injecting a reaction gas onto the substrate on which the fluorodisilazane compound or silicon-containing thin film deposition composition has been adsorbed to deposit a silicon-containing thin film.

[0028] A method for producing the silicon-containing thin film according to one embodiment may include the steps of maintaining the temperature of a substrate mounted in a chamber at 100°C or higher, and simultaneously injecting the fluorodisilazane compound represented by chemical formula 1, or the silicon-containing thin film deposition composition, and a reaction gas to deposit a silicon-containing thin film.

[0029] The deposition may be carried out by atomic layer deposition (ALD), chemical vapor deposition (CVD), metal-organic chemical vapor deposition (MOCVD), low-pressure chemical vapor deposition (LPCVD), plasma chemical vapor deposition (PECVD), or plasma atomic layer deposition (PEALD).

[0030] The silicon-containing thin film may be a fluorine and silicon-containing thin film. The fluorine and silicon-containing thin film may have a dielectric constant of 3.0 or less. [Effects of the Invention]

[0031] A fluorodisilazane compound according to one aspect of the present invention is easy to store and handle, enables the deposition of thin films with a high thin-film deposition rate, and allows for the production of high-quality silicon-containing thin films with high purity through a simple manufacturing process.

[0032] Furthermore, silicon-containing thin films produced from fluorodisilazane compounds 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 very low dielectric constant. [Brief explanation of the drawing]

[0033] [Figure 1] These are the TGA and DSC analysis results for 1,3-difluoro-1,3-dimethyl-1,3-divinyldisilazane prepared in Example 1. [Modes for carrying out the invention]

[0034] In this specification, unless otherwise defined, all technical and scientific terms have the same meaning as those generally understood by those skilled in the art in which the present invention pertains. The terms used in this specification are merely for the effective description of specific examples and are not intended to limit the present invention.

[0035] As used herein, the singular form may also include the plural form unless otherwise indicated by the context. Furthermore, the numerical ranges used herein include lower and upper limits, all values ​​within that range, increments logically derived from the form and width of the defined range, all limited values ​​among them, and all possible combinations of upper and lower limits of numerical ranges limited to different forms. Unless otherwise defined herein, values ​​outside the numerical range that may occur due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0036] The term “includes” as used herein is an open-ended statement equivalent to expressions such as “provides,” “contains,” “has,” or “characterizes,” and does not exclude any elements, materials, or processes not additionally listed.

[0037] 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 all linear or branched alkyl groups. The alkyl group may have 1 to 7 carbon atoms, more specifically 1 to 5, and more specifically 1 to 4 carbon atoms. As an example, the linear alkyl group includes methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl, and the branched alkyl group includes, but is 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-methylhexyl, 5-methylhexyl, 2,3-dimethylbutyl, 2,3-dimethylpentyl, and 2,4-dimethylpentyl.

[0038] In this specification, the term "alkenyl" means a linear or branched unsaturated hydrocarbon radical containing one or more double bonds, and the term "alkynyl" means a linear or branched unsaturated hydrocarbon radical containing one or more triple bonds.

[0039] One aspect of the present invention provides a fluorodisilazane compound that can be used as a precursor for high-quality silicon-containing thin films. Specifically, a fluorodisilazane compound according to one embodiment may be represented by the following chemical formula 1.

[0040] [ka]

[0041] (In the above chemical formula 1,

number

number

number

[0042] The fluorodisilazane compound represented by chemical formula 1 has the structural characteristics described above, which allows for the easy formation of high-purity silicon-containing thin films with a high deposition rate. Furthermore, since a silicon-containing thin film produced from a fluorodisilazane compound according to one embodiment can have a low dielectric constant, it is expected to be useful as an insulating film material for semiconductor devices.

[0043] The fluorodisilazane compound represented by the aforementioned chemical formula 1 may be represented, for example, by the following chemical formulas 2 or 3.

[0044] [ka]

[0045] [ka]

[0046] (In the above chemical formulas 2 and 3, A1 and A2 are independently either a single bond or a (C1-C7) alkylene. R1 is hydrogen, (C1-C7) alkyl, (C2-C7) alkenyl, or (C2-C7) alkynyl. R2 and R3 are independently hydrogen, fluoro, cyano, isocyanate, (C1-C7)alkyl, fluoro(C1-C7)alkyl, (C2-C7)alkenyl, fluoro(C2-C7)alkenyl, fluoro(C2-C7)alkynyl, or (C2-C7)alkynyl. R4-R9 are each independently hydrogen, fluoro, or (C1-C7) alkyl.

[0047] As an example, in chemical formulas 2 and 3, A1 and A2 are each independently a single bond or (C1-C4)alkylene, R1 is hydrogen, (C1-C4)alkyl, (C2-C4)alkenyl, or (C2-C4)alkynyl, R2 and R3 are each independently hydrogen, fluoro, cyano, isocyanate, (C1-C4)alkyl, fluoro(C1-C4)alkyl, (C2-C4)alkenyl, fluoro(C2-C4)alkenyl, fluoro(C2-C4)alkynyl, or (C2-C4)alkynyl, and R4 to R9 may each independently be hydrogen, fluoro, or (C1-C3)alkyl.

[0048] For example, in the above chemical formula 2, A1 and A2 are the same and may be a single bond or (C1-C3)alkylene, R1 may be hydrogen or (C1-C3)alkyl, and R4 to R9 may each be independently hydrogen or fluoro.

[0049] For example, in the above chemical formula 3, A1 and A2 are the same and may be a single bond or (C1-C3)alkylene, R1 may be hydrogen or (C1-C3)alkyl, and R4 and R5 are the same and may be hydrogen or (C1-C3)alkyl.

[0050] Specifically, the fluorodisilazane compound may be represented by the following chemical formula 4 or 5.

[0051] [ka]

[0052] [ka]

[0053] (In the above chemical formulas 4 and 5, R1 is hydrogen, (C1-C4) alkyl, or (C2-C4) alkenyl. R2 and R3 are, independently, hydrogen, fluoro, cyano, isocyanate, (C1-C3) alkyl, fluoro(C1-C4) alkyl, fluoro(C2-C4) alkenyl, or (C2-C4) alkenyl.

[0054] For example, R2 and R3 may each be independently hydrogen, fluoro, cyano, isocyanate, (C1-C3)alkyl, or fluoro(C1-C3)alkyl, specifically, R2 and R3 may each be independently hydrogen, fluoro, cyano, isocyanate, methyl, or -CF3.

[0055] Specifically, R2 and R3 are identical to each other and may be hydrogen, fluoro, cyano, isocyanate, methyl, or -CF3. As an example, R2 and R3 may be different from each other and may be hydrogen, fluoro, cyano, isocyanate, methyl, or -CF3.

[0056] The fluorodisilazane compound according to one embodiment may be selected from, but is not necessarily limited to, the following compounds. [ka]

[0057] The following describes in detail a method for producing the fluorodisilazane compound represented by chemical formula 1 according to one embodiment. However, it goes without saying that synthesis by other methods that are generally recognizable to those skilled in the art is also possible, and the organic solvent used is not limited, and the reaction time and temperature can also be changed within the scope that does not deviate from the core of the present invention.

[0058] A method for producing the fluorodisilazane compound represented by chemical formula 1 according to one embodiment may include the steps of (A) reacting a compound represented by the following chemical formula 11 with compounds represented by the following chemical formulas 12 and 13 to produce a compound represented by the following chemical formula 14, and (B) substituting Cl with F in the compound represented by the following chemical formula 14 to produce the fluorodisilazane compound of chemical formula 1.

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] (Among the above chemical formulas 11-14, R'2 and R'3 are independently hydrogen, Cl, cyano, isocyanate, (C1-C7)alkyl, fluoro(C1-C7)alkyl, (C2-C7)alkenyl, fluoro(C2-C7)alkenyl, fluoro(C2-C7)alkynyl, or (C2-C7)alkynyl.

number

[0064] Step (A) may be carried out at 50-200°C for 1-10 hours, specifically at 50-150°C for 1-8 hours, but is not limited to this and can be modified depending on the type and amount of reactants and solvent used.

[0065] Step (B) may be carried out by providing a fluoride source, which may be selected from, but is not limited to, alkali metal fluorides such as LiF, KF, NaF, RbF, and 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, and SbF3.

[0066] Furthermore, step (B) may be carried out at 50-200°C for 1-10 hours, specifically at 50-150°C for 1-8 hours, but is not limited to this and can be modified depending on the type and amount of reactants and solvent used.

[0067] Furthermore, one aspect of the present invention provides a silicon-containing thin film deposition composition comprising the fluorodisilazane compound. The silicon-containing thin film deposition composition according to one aspect always contains the fluorodisilazane 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.

[0068] One 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 fluorodisilazane compound represented by the following chemical formula 1, or a silicon-containing thin film deposition composition containing the same, and a reaction gas.

[0069] [ka]

[0070] (In the above chemical formula 1,

number

[0071] A method for producing a silicon-containing thin film according to one embodiment involves using a composition containing a fluorodisilazane compound represented by chemical formula 1 as a precursor, thereby enabling the production of a high-quality silicon-containing thin film with a high deposition rate even at low power, and the silicon-containing thin film can further contain fluorine. For example, by adjusting conditions such as the deposition temperature during deposition, it is possible to provide a fluorine and silicon-containing thin film by allowing the fluorine (F) of the fluorodisilazane compound to remain in the thin film.

[0072] The fluorodisilazane compound according to one embodiment of the present invention has the advantage of being able to produce a thin film containing both fluorine and silicon using a single precursor. In other words, generally, fluorine and silicon-containing thin films are produced by first manufacturing 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 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.

[0073] In a method for producing a silicon-containing thin film according to one aspect of the present invention, the fluorodisilazane compound and the reaction gas may be supplied organically or independently of each other. Furthermore, the fluorodisilazane compound and the reaction gas may be supplied continuously or discontinuously, and the discontinuous supply may include the form of a pulse.

[0074] As an example, the method for manufacturing the silicon-containing thin film is as follows: a) A step of maintaining the temperature of the substrate installed inside the chamber at 100°C or higher, b) The step of adsorbing a fluorodisilazane compound represented by chemical formula 1, or a silicon-containing thin film deposition composition, onto a substrate, c) The step of injecting a reaction gas onto a substrate on which the fluorodisilazane compound or silicon-containing thin film deposition composition is adsorbed, thereby depositing a silicon-containing thin film.

[0075] Specifically, the method for manufacturing the silicon-containing thin film is as follows: a) A step of maintaining the temperature of the substrate installed inside the chamber at 100°C or higher, b) The step of adsorbing a fluorodisilazane compound represented by chemical formula 1, or a silicon-containing thin film deposition composition, onto a substrate, c) A step of purging residual fluorodisilazane compounds, or residual vapor deposition compositions and by-products, d) A step of injecting a reaction gas into a substrate on which the fluorodisilazane compound or silicon-containing thin film deposition composition is adsorbed to form a silicon-containing thin film, e) The step of purging residual reaction gases and by-products may be included.

[0076] Furthermore, as an example, the method for manufacturing the silicon-containing thin film is as follows: The steps include maintaining the temperature of the substrate mounted inside the chamber at 100°C or higher, The process may include the step of simultaneously injecting a reaction gas with a fluorodisilazane compound represented by the aforementioned chemical formula 1, or a silicon-containing thin film deposition composition, to deposit a silicon-containing thin film.

[0077] The deposition method is not particularly limited as long as it is commonly used in the field, but may, for example, be 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), but is not limited thereto.

[0078] The type of reaction gas is not particularly limited as long as it is commonly used in the field, but may include, for example, 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), acetic anhydride ((CH3CO)2O), or a combination thereof. The purging gas may be nitrogen (N2), argon (Ar), helium (He), or a combination thereof.

[0079] The substrate is not particularly limited as long as it is commonly used in the field, but may include, 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; or 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.

[0080] Furthermore, in addition to directly forming the silicon-containing thin film on the substrate, multiple conductive layers, dielectric layers, or insulating layers may be further formed between the substrate and the silicon-containing thin film.

[0081] 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. For example, the reaction gas may be supplied after being activated by generating a plasma at 50-1,000 W, 100-800 W, or 400-600 W.

[0082] In other words, a method for manufacturing a silicon-containing thin film according to one embodiment allows for the effective production of a thin film even at low temperatures and with low plasma generation by using the compound of chemical formula 1 as a precursor.

[0083] Furthermore, one aspect of the present invention provides a silicon-containing thin film produced by the above-described manufacturing method. A silicon-containing thin film according to one embodiment can be any thin film that can be manufactured within the range recognizable to a person skilled in the art, and specifically, it may be a silicon fluoride carbide film, a silicon fluoride oxide film, a silicon fluoride film, a silicon carbide film, a silicon oxide film, a silicon nitride film, a silicon carbonitride film, and various other high-quality thin films containing silicon, or fluorine and silicon, within the range recognizable to a person skilled in the art can be manufactured.

[0084] Because the silicon-containing thin film exhibits excellent chemical and thermal stability, it can be used in 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.

[0085] The embodiments described above will be explained in more detail below with reference to examples. However, the following examples are for illustrative purposes only and do not limit the scope of rights. The physical properties of the examples were measured as follows.

[0086] 1) Thickness The thickness of fluorine and silicon-containing thin films was measured using an ellipsometer (OPTI-PROBE 2600, THERMA-WAVE).

[0087] 2) Thermal properties Thermogravimetric analysis (TGA, L81-II, LINSEIS) and differential scanning calorimeter (DSC) were performed to measure the thermal stability, volatility, and decomposition temperature of fluorodisilazane compounds.

[0088] <Synthesis of fluorodisilazane compounds> [Example 1] Synthesis of 1,3-difluoro-1,3-dimethyl-1,3-divinyldisilazane

[0089] [ka]

[0090] After setting up a Dean Stark reflux apparatus in a flame-dried 2 L flask under anhydrous and inert atmosphere, 360 g (2.23 mol) of hexamethyldisilazane and 660 g (4.68 mol) of dichloromethylvinylsilane were added, and the by-product chlorotrimethylsilane was recovered by heating at 80-120°C. The mixture was heated and stirred for approximately 8 hours until no more chlorotrimethylsilane was produced or recovered. After gradually cooling to room temperature, 363 g (85% yield, 1.26 mol) of 1,3-dichloro-1,3-dimethyl-1,3-divinyldisilazane was recovered from the reaction mixture at 50°C at 1 torr.

[0091] In a 2 L flask, flame-dried under anhydrous and inert atmosphere, 122 g (4.68 mol) of LiF and 1126 g (15.61 mol) of tetrahydrofuran (THF) were added. 363 g (1.56 mol) of 1,3-dichloro-1,3-dimethyl-1,3-divinyldisilazane, prepared earlier, was gradually added at room temperature. The internal temperature was maintained below 40°C during the addition. After the addition was complete, the reaction was completed by stirring at 70°C for 8 hours. After filtering the reaction mixture, the solvent THF was removed by simple distillation at 70-80°C at 760 torr, and then the mixture was distilled under reduced pressure at 30-31°C at 5 torr to obtain 157 g (0.78 mol) of the target compound, 1,3-difluoro-1,3-dimethyl-1,3-divinyldisilazane (yield 50%, GC purity 99%).

[0092] 1 H-NMR(CDCl3): 0.30ppm(m, 6H, Si-CH3), 1.85ppm(br, 1H, Si-NH-Si), 5.9~6.1ppm(m, 6H, Si-CH=CH2) 29 Si-NMR(CDCl3): -7.85ppm(d, 2Si)

[0093] [Example 2] Synthesis of 1,1,3,3-tetrafluoro-1,3-divinyldisilazane

[0094] [ka]

[0095] After setting up a Dean-Stark reflux apparatus in a flame-dried 2 L flask under anhydrous and inert atmosphere, 300 g (1.86 mol) of hexamethyldisilazane and 526 g (3.26 mol) of trichlorovinylsilane were added, and the by-product chlorotrimethylsilane was collected by heating at 80-120°C. The mixture was heated and stirred for approximately 8 hours until no further chlorotrimethylsilane was produced. The reaction mixture was gradually cooled to room temperature, and 149 g (50% yield, 0.56 mol) of 1,1,3,3-tetrachloro-1,3-divinyldisilazane was collected from the reaction mixture at 44°C at 1 torr.

[0096] In a 1 L flask, flame-dried under anhydrous and inert atmosphere, 65 g (2.51 mol) of LiF and 240 g (2.51 mol) of tetrahydrofuran (THF) were added. 149 g (0.56 mol) of the previously prepared 1,1,3,3-tetrachloro-1,3-divinyldisilazane was gradually added at room temperature. The internal temperature was maintained below 40°C during the addition. After the addition was complete, the reaction was completed by stirring at 70°C for 8 hours. After filtering the reaction mixture, the solvent THF was removed from the filtrate by simple distillation at 70-80°C at 760 torr, and then the filtrate was distilled under reduced pressure at 50°C at 0.94 torr to obtain 56 g (0.28 mol) of the target compound, 1,1,3,3-tetrafluoro-1,3-divinyldisilazane (yield 50%, GC purity 95%).

[0097] 1 H-NMR(CDCl3): 2.53ppm(br, 1H, Si-NH-Si), 6.14~6.32ppm(m, 6H, Si-CH=CH2) 29 Si-NMR(CDCl3): -48.84ppm(t, 2Si)

[0098] Figure 1 shows the thermogravimetric (TGA) and differential scanning calorimetry (DSC) analysis results for 1,3-difluoro-1,3-dimethyl-1,3-divinyldisilazane produced in Example 1. Referring to Figure 1, it can be seen that the compound from Example 1 has a single evaporation stage at approximately 150°C and exhibits rapid vaporization characteristics with almost no residual mass at 300°C. These results indicate that the 1,3-difluoro-1,3-dimethyl-1,3-divinyldisilazane compound from Example 1 has excellent thermal stability.

[0099] [Example 3] Thermal atomic layer deposition (TALD) using the compound from Example 1 In a conventional thermal atomic layer deposition (TALD) apparatus using the TALD method, 1,3-difluoro-1,3-dimethyl-1,3-divinyldisilazane (as described in [Example 1]) was used as a silicon-containing thin film deposition precursor for forming a silicon oxide film, and the thin film was evaluated at 630°C. Oxygen and hydrogen were used as reaction gases, and argon was used as the purge gas.

[0100] The silicon substrate was set to a temperature of 630°C, and the silicon precursor shown in Table 1 below was filled into a stainless steel bubbler container and maintained at 35°C. First, the silicon precursor vaporized in the stainless steel bubbler container was transferred to the silicon substrate for 0.5 to 10 seconds using 100 sccm of argon gas as a carrier gas to allow it to adsorb onto the silicon substrate. Second, 1,000 sccm of argon gas was used to remove any silicon precursor that had not been adsorbed for approximately 10 seconds. Third, 4,000 sccm of oxygen, or 4,000 sccm of oxygen and 1,000 sccm of hydrogen, was flowed as a reaction gas for 5 seconds to form a silicon oxide film. Finally, 1,000 sccm of argon gas was used to remove reaction byproducts and residual reaction gases for approximately 10 seconds. The above process constituted one cycle, and a silicon oxide film was formed by repeating a certain number of cycles. Table 1 shows specific methods for depositing silicon oxide films.

[0101] [Table 1]

[0102] [Example 4] Thermochemical vapor deposition (TCVD) using the compound from Example 1 In a conventional thermochemical vapor deposition (TCVD) apparatus using the TCVD method, 1,3-difluoro-1,3-dimethyl-1,3-divinyldisilazane (as described in [Example 1]) was used as a silicon-containing thin film deposition precursor for forming a silicon oxide film, and the thin film was evaluated at 630°C. Oxygen and hydrogen were used as reaction gases, and argon was used as the base gas.

[0103] The silicon substrate was set to a temperature of 630°C, and the silicon precursor shown in Table 3 below was packed into a stainless steel bubbler container and maintained at 35°C. First, the silicon precursor vaporized in the stainless steel bubbler container was transferred to the silicon substrate for 5 minutes using 100 sccm of argon gas as a carrier gas to allow it to adsorb onto the silicon substrate. At the same time, a silicon oxide film was formed by flowing 4000 sccm of oxygen, 4000 sccm of ammonia, or 4000 sccm of oxygen and 1000 sccm of hydrogen as reaction gases. Table 2 shows specific methods for depositing silicon oxide films.

[0104] [Table 2]

[0105] Although the present invention has been described above with reference to specific details, limited examples, and comparative examples, these are provided only for a more general understanding of the invention, and the invention is not limited to the above examples. Various modifications and variations can be made from this description by those with ordinary skill in the art to which the invention pertains.

[0106] Therefore, the concept of the present invention should not be limited to the embodiments described, and any equivalent or equivalent modifications to the appended claims, as well as the claims themselves, can be said to fall within the scope of the concept of the present invention.

Claims

1. A fluorodisilazane compound represented by the following chemical formula 1. 【number】 In the aforementioned chemical formula 1, [Math 1] It is a double bond or a triple bond, [Math 2] If R is a triple bond, ６ ~R ９ It does not exist. [Math 3] If R is a double bond, ６ ~R ９ These are, independently, hydrogen, fluoro, fluoro(C1-C7)alkyl, or (C1-C7)alkyl, A １ and A ２ Each of these is independently a single bond or a (C1-C7) alkylene. R １ is hydrogen, (C1-C7) alkyl, (C2-C7) alkenyl, or (C2-C7) alkynyl, R ２ and R ３ are each independently hydrogen, fluoro, cyano, isocyanate, (C1-C7)alkyl, fluoro(C1-C7)alkyl, (C2-C7)alkenyl, fluoro(C2-C7)alkenyl, fluoro(C2-C7)alkynyl, or (C2-C7)alkynyl, R ４ and R ５ These are, independently, hydrogen, fluoro, fluoro(C1-C7)alkyl, or (C1-C7)alkyl.

2. A fluorodisilazane compound according to claim 1, represented by the following chemical formula 2 or 3. 【Chemistry 2】 【Transformation 3】 In the aforementioned chemical formulas 2 and 3, A １ and A ２ Each of these is independently a single bond or a (C1-C4) alkylene. R １ is hydrogen, (C1-C4) alkyl, (C2-C4) alkenyl, or (C2-C4) alkynyl, R ２ and R ３ Each of these is independently hydrogen, fluoro, cyano, isocyanate, (C1-C4)alkyl, fluoro(C1-C4)alkyl, (C2-C4)alkenyl, fluoro(C2-C4)alkenyl, fluoro(C2-C4)alkynyl, or (C2-C4)alkynyl. R ４ ~R ９ These are, independently, hydrogen, fluoro, fluoro(C1-C4)alkyl, or (C1-C4)alkyl.

3. A fluorodisilazane compound according to claim 1, represented by the following chemical formula 4 or 5. 【Chemistry 4】 【Transformation 5】 In the aforementioned chemical formulas 4 and 5, R １ is hydrogen, (C1-C4) alkyl, or (C2-C4) alkenyl, R ２ and R ３ These are, independently, hydrogen, fluoro, cyano, isocyanate, (C1-C4)alkyl, fluoro(C1-C4)alkyl, fluoro(C2-C4)alkenyl, or (C2-C4)alkenyl.

4. A fluorodisilazane compound according to claim 1, selected from the following compounds. 【Transformation 6】

5. A silicon-containing thin film deposition composition comprising the fluorodisilazane compound described in any one of claims 1 to 4.

6. A method for producing a silicon-containing thin film, comprising the step of depositing a silicon-containing thin film using a fluorodisilazane compound represented by the following chemical formula 1, or a silicon-containing thin film deposition composition containing the same. 【number】 In the aforementioned chemical formula 1, [Math 4] , R １ ~R ９ A １ , and A ２ This is the same as the definition in claim 1.

7. The steps include maintaining the temperature of the substrate installed inside the chamber at 100°C or higher, The process involves adsorbing a fluorodisilazane compound represented by chemical formula 1, or a silicon-containing thin film deposition composition, onto a substrate. A method for producing a silicon-containing thin film according to claim 6, comprising the step of injecting a reaction gas into a substrate on which the fluorodisilazane compound or the silicon-containing thin film deposition composition is adsorbed, thereby depositing a silicon-containing thin film.

8. The steps include maintaining the temperature of the substrate installed inside the chamber at 100°C or higher, A method for producing a silicon-containing thin film according to claim 6, comprising the step of simultaneously injecting a reaction gas with a fluorodisilazane compound represented by the chemical formula 1, or a silicon-containing thin film deposition composition, to deposit a silicon-containing thin film.

9. The method for producing a silicon-containing thin film according to claim 6, wherein the deposition is carried out by atomic layer deposition (ALD), chemical vapor deposition (CVD), metal-organic chemical vapor deposition (MOCVD), low-pressure chemical vapor deposition (LPCVD), plasma chemical vapor deposition (PECVD), or plasma atomic layer deposition (PEALD).

10. The method for producing a silicon-containing thin film according to claim 6, wherein the silicon-containing thin film is a fluorine and silicon-containing thin film.

11. The method for producing a silicon-containing thin film according to claim 10, wherein the fluorine and silicon-containing thin film has a dielectric constant of 3.0 or less.

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