Cyclosilazane compound and method of producing silicon-containing thin film using the same

Abstract

To provide a cyclosilazane compound and a composition for silicon-containing thin film deposition as a low dielectric silicon-containing thin film precursor of high quality which may be usefully applied as an insulating film of a semiconductor device, in particular, a spacer of a semiconductor miniaturization process not only due to advantages of being excellent in both chemical stability and thermal stability but also by having a low dielectric constant.SOLUTION: A cyclosilazane compound is expressed by the following chemical formula in which X is halogen, R1 to R3 are independently hydrogen, halogen, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl, R4 is halogen, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl or -Si(R11)(R12)(R13), A is -(CR7R8)n-, R5 to R8 and R11 to R13 are independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl, and n is an integer from 1 to 5.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a cyclosilazane compound used as a precursor for a low-dielectric 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 technology]

[0002] Silicon thin films, produced by various deposition methods such as atomic layer deposition (ALD) and chemical vapor deposition (CVD), are used in semiconductor technology as semiconductor substrates, diffusion masks, oxidation prevention films, dielectric films, insulating films, etc.

[0003] Meanwhile, it is very important that insulating films for spacers in semiconductor devices have a low dielectric constant and excellent etching resistance. Furthermore, in order to be applicable to actual processes, they must also satisfy conditions such as ease of processing, excellent chemical stability, and excellent thermal stability. Therefore, the required physical properties of insulating films for spacers to be applied to next-generation semiconductor devices are gradually becoming more stringent.

[0004] For this reason, research into lowering the dielectric constant of silicon thin films has been ongoing, but the results have either not been sufficiently low, or have resulted in reduced thermal stability and etching resistance, and low thin film formation speeds, resulting in reduced productivity. Another method proposed to simultaneously achieve low dielectric constants and etching resistance for silicon thin films is to dope fluorine (F) after the formation of a silicon-containing thin film. However, this method requires an additional fluorine doping step, making the process complicated, and doping occurs primarily around the surface of the thin film, with F doping difficult in regions deeper than the surface, resulting in reduced film quality. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent Publication No. 10-2002-0063196 (2002.08.01.) Summary of the Invention [Problem to be solved by the invention]

[0006] One aspect of the present invention provides a cyclosilazane compound as a high-quality low-dielectric silicon-containing thin film precursor, and a composition for depositing a silicon-containing thin film containing the same.

[0007] Another aspect of the present invention provides a method for producing a silicon-containing thin film, which allows for deposition of a thin film at a high deposition rate even under mild conditions, and can produce a high-quality thin film with a high yield. [Means for solving the problem]

[0008] One aspect of the present invention provides a cyclosilazane compound represented by the following Chemical Formula 1: [Chemical formula 1] [ka] (In the above Chemical Formula 1, X is a halogen; R1 to R3 are each independently hydrogen, halogen, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; R4 is hydrogen, halogen, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, or -Si(R 11 )(R 12 )(R 13 ) and A is -(CR7R8) n - and R5 to R8 and R 11 ~R 13 are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; n is an integer from 1 to 5.

[0009] wherein X is fluoro, R1 to R3 are each independently hydrogen, fluoro, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl, and R4 is hydrogen, fluoro, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or -Si(R 11 )(R 12 )(R 13 ) and A is -(CR7R8) n - and R5 to R8 and R 11 ~R 13 are each independently hydrogen, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl, and n may be an integer from 1 to 3.

[0010] According to one embodiment, the cyclosilazane compound may be represented by the following Chemical Formula 2: [Chemical formula 2] [ka] (In the above Chemical Formula 2, R1 to R3 are each independently hydrogen, fluoro, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; R4 is hydrogen, fluoro, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, or -Si(R 11 )(R 12 )(R 13 ) and R 11 ~R 13 are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; n is an integer from 1 to 5.

[0011] The R1 to R3 are each independently hydrogen, fluoro, or C1-C4 alkyl, and R4 is hydrogen, fluoro, C1-C4 alkyl, or —Si(R 11 )(R 12 )(R 13 ) and R 11 ~R 13are each independently hydrogen or C1-C4 alkyl, and n may be an integer from 1 to 3.

[0012] According to one embodiment, the cyclosilazane compound may be represented by the following Formula 3: [Chemical formula 3] [ka] (In the above Chemical Formula 3, R1 and R3 are each independently hydrogen, fluoro, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; R4 is hydrogen, fluoro, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, or -Si(R 11 )(R 12 )(R 13 ) and R 11 ~R 13 are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; n is an integer from 1 to 5.

[0013] wherein R1 and R3 are each independently hydrogen, fluoro, or C1-C4 alkyl, and R4 is hydrogen, fluoro, C1-C4 alkyl, or -Si(R 11 )(R 12 )(R 13 ) and R 11 ~R 13 are each independently hydrogen or C1-C4 alkyl, and n may be an integer from 1 to 3.

[0014] According to one embodiment, the cyclosilazane compound may be selected from the following structures: [ka]

[0015] Yet another aspect of the present invention provides a composition for depositing silicon-containing thin films, comprising a cyclosilazane compound.

[0016] In yet another aspect, the present invention provides a method for producing a silicon-containing thin film using a cyclosilazane compound represented by the following Chemical Formula 1 or a composition for depositing a silicon-containing thin film containing the same: [Chemical formula 1] [ka] (In the above Chemical Formula 1, R1 to R6, X and A are the same as defined above.)

[0017] The silicon-containing thin film may be a fluorine and silicon-containing thin film.

[0018] The silicon-containing thin film may contain 0.5 at % or more of fluorine. [Effects of the Invention]

[0019] The cyclosilazane compound according to one embodiment of the present invention has excellent thermal stability, and therefore, it is possible to deposit a thin film at a high thin film deposition rate even at low temperatures, and to produce a high-quality silicon-containing thin film with high purity through a simple manufacturing process.

[0020] Furthermore, a silicon-containing thin film prepared from a cyclosilazane compound according to one embodiment has excellent chemical and thermal stability as well as a very low dielectric constant, and is therefore expected to be useful as an insulating film for semiconductor devices, particularly as a spacer in semiconductor miniaturization processes. [Brief explanation of the drawings]

[0021] [Figure 1] 1 shows the results of TGA and DSC analysis of 2,2,5,5-tetrafluoro-1-isopropyl-[1,2,5]azadisilacyclopentane prepared in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0022] Unless otherwise defined herein, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used in the description herein are merely for the purpose of effectively describing particular embodiments and are not intended to limit the present invention.

[0023] As used herein, the singular forms "a," "an," and "the" can be intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0024] Throughout this specification, "comprising," "comprising," "containing," or "having" an element means that it may further include other elements, but does not exclude unrecited elements, materials, or steps, unless specifically stated to the contrary.

[0025] Numerical ranges used herein include lower and upper limits, all values ​​within the range, increments logically derived from the form and width of the defined range, and all possible combinations of upper and lower limits of numerical ranges defined in different forms, including all values ​​bounded therein. Unless otherwise specified herein, values ​​outside the numerical ranges that may occur due to experimental error or rounding of values ​​are also included in the defined numerical ranges.

[0026] Unless otherwise defined herein, "about" is understood to mean a value within 30%, 25%, 20%, 15%, 10% or 5% of the specified value.

[0027] As used herein, the term "alkyl" refers to an organic radical derived from an aliphatic hydrocarbon by removal of one hydrogen, and can include both straight-chain and branched alkyls. The alkyl can have 1 to 7, specifically 1 to 5, and specifically 1 to 4 carbon atoms. Examples of straight-chain alkyls include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl, while examples of branched alkyls 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, 4-methylhexyl, 5-methylhexyl, 2,3-dimethylbutyl, 2,3-dimethylpentyl, and 2,4-dimethylpentyl.

[0028] As used herein, the term "alkenyl" means a straight-chain or branched unsaturated hydrocarbon radical containing one or more double bonds, and "alkynyl" means a straight-chain or branched unsaturated hydrocarbon radical containing one or more triple bonds.

[0029] The present disclosure will now be described in detail, but by way of example only, and is not intended to be limited to the specific embodiments illustratively described.

[0030] One aspect of the present invention provides cyclosilazane compounds for use as precursors for high-quality low-dielectric silicon-containing thin films.

[0031] Specifically, the cyclosilazane compound according to one embodiment may be represented by the following Chemical Formula 1:

[0032] [Chemical formula 1] [ka]

[0033] (In the above Chemical Formula 1, X is a halogen; R1 to R3 are each independently hydrogen, halogen, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; R4 is hydrogen, halogen, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, or -Si(R 11 )(R 12 )(R 13 ) and A is -(CR7R8) n - and R5 to R8 and R 11 ~R 13 are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; n is an integer of 1 to 5, and when n is an integer of 2 or more, R7 and R8 may be different from each other.

[0034] According to one embodiment, the cyclosilazane compound has the structural features of Formula 1, e.g., a ring structure including a disilazane group (*-Si-N-Si-*) and at least one halogen (F, Cl, Br, I) substituent. Therefore, the cyclosilazane compound exists in a liquid state at room temperature and has excellent volatility and thermal stability. This enables deposition of a thin film at a high thin film deposition rate even at low temperatures, and can provide a low-dielectric thin film with high purity and excellent durability.

[0035] As an example, X may be fluoro (-F).

[0036] For example, R1 to R3 are each independently hydrogen, fluoro, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl, and R4 is hydrogen, fluoro, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or -Si(R 11 )(R 12 )(R 13 ) and A is -(CR7R8) n - and R5 to R8 and R 11 ~R 13are each independently hydrogen, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl, and n may be an integer from 1 to 3.

[0037] Specifically, the cyclosilazane compound according to one embodiment may be represented by the following Chemical Formula 2:

[0038] [Chemical formula 2] [ka]

[0039] (In the above Chemical Formula 2, R1 to R3 are each independently hydrogen, fluoro, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; R4 is hydrogen, fluoro, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, or -Si(R 11 )(R 12 )(R 13 ) and R 11 ~R 13 are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; n is an integer from 1 to 5.

[0040] For example, R1 to R3 are each independently hydrogen, fluoro, or C1-C4 alkyl, and R4 is hydrogen, fluoro, C1-C4 alkyl, or -Si(R 11 )(R 12 )(R 13 ) and R 11 ~R 13 are each independently hydrogen or C1-C4 alkyl, and n may be an integer from 1 to 3.

[0041] Specifically, the cyclosilazane compound according to one embodiment may be represented by the following Chemical Formula 3:

[0042] [Chemical formula 3] [ka]

[0043] (In the above Chemical Formula 3, R1 and R3 are each independently hydrogen, fluoro, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; R4 is hydrogen, fluoro, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, or -Si(R 11 )(R 12 )(R 13 ) and R 11 ~R 13 are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; n is an integer from 1 to 5.

[0044] For example, in Formula 3, R1 and R3 are each independently hydrogen, fluoro, or C1-C4 alkyl, and R4 is hydrogen, fluoro, C1-C4 alkyl, or -Si(R 11 )(R 12 )(R 13 ) and R 11 ~R 13 are each independently hydrogen or C1-C4 alkyl, and n may be an integer from 1 to 3.

[0045] As an example, R1 and R3 may each independently be hydrogen, fluoro, or methyl.

[0046] As an example, R1 and R3 are the same as each other and may be hydrogen, fluoro or C1-C4 alkyl, or methyl.

[0047] In one example, R4 is hydrogen, fluoro, C1-C4 alkyl, or -Si(R 11 )(R 12 )(R 13 ) and R 11 ~R 13are each independently hydrogen or C1-C4 alkyl, and n may be an integer from 1 to 3.

[0048] As an example, the above-mentioned R 11 ~R 13 are the same as each other and may be hydrogen or C1-C4 alkyl, or methyl.

[0049] In one example, R4 is hydrogen, fluoro, branched (C3-C7) alkyl, or -Si(R 11 )(R 12 )(R 13 ), for example, the branched (C3-C7) alkyl may be isopropyl, sec-butyl, isobutyl, tert-butyl, or isopentyl.

[0050] As an example, n may be 1 or 2.

[0051] The cyclosilazane compound according to one embodiment may be selected from the following structures, but is not limited thereto.

[0052] [ka]

[0053] Hereinafter, a method for preparing the cyclosilazane compound represented by Formula 1 according to one embodiment will be described in detail. However, it goes without saying that other synthesis methods recognizable by those skilled in the art are also possible. The organic solvent used here is not limited, and the reaction time and temperature can also be changed within the scope of the invention.

[0054] According to one embodiment, a method for producing a cyclosilazane compound represented by Formula 1 may include the step of (A) reacting a compound represented by Formula 11 with a compound represented by Formula 12:

[0055] [Chemical formula 11] [ka]

[0056] [Chemical formula 12] [ka]

[0057] (In the above chemical formulas 11 and 12, Y1 and Y2 are each independently Cl or Br; R1 to R6, X, and A are the same as defined in Chemical Formula 1.

[0058] In addition, the method for preparing the cyclosilazane compound represented by Formula 1 according to one embodiment may further include step (B) of reacting a fluorine source after step (A).

[0059] The step (A) is carried out at 0 to 30°C for 1 to 10 hours, specifically at 10 to 30°C for 1 to 5 hours, but is not limited thereto and can be changed depending on the reactants, the type and amount of solvent used.

[0060] The fluorine source 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.

[0061] Furthermore, step (B) is carried out at 30 to 70°C for 5 to 20 hours, specifically at 40 to 60°C for 10 to 20 hours, but is not limited thereto and can be changed depending on the type and amount of reactant and solvent used.

[0062] Yet another aspect of the present invention provides a composition for depositing a silicon-containing thin film, comprising the cyclosilazane compound.

[0063] A composition for depositing a silicon-containing thin film according to one embodiment includes a cyclosilazane compound represented by Chemical Formula 1 as a precursor for depositing a thin film, and the content of the compound represented by Chemical Formula 1 in the composition may be within a range that would be recognizable by a person skilled in the art, taking into consideration the film formation conditions, the thickness of the thin film, the properties of the thin film, and the use of the thin film.

[0064] In yet another aspect, the present invention provides a method for producing a silicon-containing thin film using a cyclosilazane compound represented by the following Chemical Formula 1 or a composition for depositing a silicon-containing thin film containing the same:

[0065] [Chemical formula 1] [ka]

[0066] (In the above Chemical Formula 1, R1 to R6, X, and A are the same as defined in Chemical Formula 1.

[0067] According to one embodiment, a method for manufacturing a silicon-containing thin film uses a cyclosilazane compound represented by Formula 1 as a precursor, thereby enabling the manufacture of a high-quality silicon-containing thin film at a high deposition rate even at low temperatures and low power.

[0068] Specifically, the silicon-containing thin film according to one embodiment may be a thin film containing fluorine and silicon. In the method for manufacturing a silicon-containing thin film according to one embodiment, when the cyclosilazane compound represented by Chemical Formula 1 contains fluorine (F), the fluorine (F) of the cyclosilazane compound remains in the thin film, thereby providing a high-quality fluorine- and silicon-containing thin film with a low dielectric constant.

[0069] Specifically, the silicon-containing thin film according to one embodiment may contain fluorine in an amount of 0.5 at% or more, or 1.0 at% or more, or 1.5 at% or more, or 2.0 at% or more, or 2.5 at% or more, or 10 at% or less, or 9 at% or less, or 8 at% or less, or 7 at% or less.

[0070] A cyclosilazane compound according to one embodiment has the advantage that a thin film containing both fluorine and silicon can be produced using a single precursor. That is, a fluorine- and silicon-containing thin film is generally produced by doping the silicon-containing thin film with fluorine using a fluorine-containing precursor, but this has the disadvantage of non-uniform fluorine content within the thin film. On the other hand, the method for producing a silicon-containing thin film according to the present invention overcomes this disadvantage and allows the production of a fluorine- and silicon-containing thin film having a uniform fluorine content using a single precursor.

[0071] In one embodiment of the method for manufacturing a silicon-containing thin film, the cyclosilazane compound and the reaction gas may be supplied organically or independently from each other. The cyclosilazane compound and the reaction gas may be supplied continuously or discontinuously, and discontinuous supply may include a pulsed supply.

[0072] As an example, the method for producing the silicon-containing thin film includes: a) maintaining a temperature of a substrate mounted in a chamber at 100° C. or higher; b) adsorbing the cyclosilazane compound represented by Formula 1 or a composition for depositing a silicon-containing thin film containing the cyclosilazane compound on a substrate; c) depositing a silicon-containing thin film by injecting a reaction gas onto the substrate on which the cyclosilazane compound or the composition for depositing a silicon-containing thin film containing the cyclosilazane compound is adsorbed.

[0073] Specifically, the method for producing the silicon-containing thin film includes the steps of: a) maintaining a temperature of a substrate mounted in a chamber at 100° C. or higher; b) adsorbing the cyclosilazane compound represented by Formula 1 or a silicon-containing thin film deposition composition containing the same onto a substrate; c) purging residual cyclosilazane compounds or residual thin film deposition compositions and by-products; d) injecting a reaction gas onto the substrate onto which the cyclosilazane compound or the thin film deposition composition containing the same is adsorbed, thereby forming a silicon-containing thin film; e) purging residual reaction gases and by-products.

[0074] Further, as an example, the method for producing the silicon-containing thin film includes the steps of: maintaining the temperature of the substrate mounted in the chamber at 100°C or higher; The method may include depositing a silicon-containing thin film by simultaneously injecting the cyclosilazane compound represented by Formula 1 or a composition for depositing a silicon-containing thin film containing the cyclosilazane compound and a reaction gas.

[0075] The deposition method is not particularly limited as long as it is a method commonly used in the art, and examples thereof include, but are not limited to, thermal chemical vapor deposition (TCVD), 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), and plasma enhanced atomic layer deposition (PEALD).

[0076] The type of the reactive gas is not particularly limited as long as it is commonly used in the field, but examples include oxygen (O), ozone (O), oxygen plasma, hydrogen (H), hydrogen plasma, water (H0), hydrogen peroxide (H0), nitrogen dioxide (NO), nitric oxide (NO), nitrous oxide (NO), ammonia (NH), carbon dioxide (CO), formic acid (HCOOH), acetic acid (CHCOOH), acetic anhydride ((CHCO)0), or a combination thereof. The purge gas may be nitrogen (N), argon (Ar), helium (He), or a combination thereof.

[0077] The substrate is not particularly limited as long as it is one that is commonly used in the relevant field, and may be, for example, a substrate containing one or more semiconductor materials selected from the group consisting of Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP, an SOI (Silicon On Insulator) substrate, a quartz substrate, a glass substrate for a display, or a flexible plastic substrate such as polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES), or polyester.

[0078] In addition, the silicon-containing thin film may be formed directly on the substrate, or a plurality of conductive layers, dielectric layers, or insulating layers may be formed between the substrate and the silicon-containing thin film.

[0079] For example, the temperature of the substrate may be adjusted to 100 to 1,000°C, or 300 to 1,000°C, or 500 to 1,000°C. Under these temperature conditions, fluorine (F) of the cyclosilazane compound represented by Chemical Formula 1 may remain in the thin film, thereby providing a high-quality fluorine- and silicon-containing thin film and a thin film with a lower dielectric constant.

[0080] For example, the reactive gas may be supplied after being activated by generating plasma at 50 to 1,000 W, or 100 to 800 W, or 400 to 600 W.

[0081] That is, in one embodiment of the method for manufacturing a silicon-containing thin film, the compound of Formula 1 is used as a precursor, thereby enabling effective manufacturing of a thin film even at low temperatures and with low plasma generation.

[0082] Another aspect of the present invention provides a silicon-containing thin film manufactured by the manufacturing method.

[0083] The silicon-containing thin film according to one embodiment may be any thin film that can be produced within the scope of recognition by a person skilled in the art in this technical field, and specifically may be a silicon fluoride carbide film, a silicon fluoride oxide film, a silicon fluoride film, a silicon carbide film, etc. In addition, various high-quality silicon-containing thin films can be produced within the scope of recognition by a person skilled in the art.

[0084] According to one embodiment, the silicon-containing thin film has excellent chemical and thermal stability as well as a very low dielectric constant, and can be used in a variety of applications, such as insulating films, diffusion barriers, spacers, intermetal dielectrics, and passivation layers in the fabrication of electronic devices.

[0085] The above-described embodiments will now be described in more detail with reference to examples, which are provided for illustrative purposes only and are not intended to limit the scope of the invention.

[0086] The physical properties of the examples were measured as follows.

[0087] 1) Thermal properties To measure the thermal stability, volatility, and decomposition temperature of the cyclosilazane compounds, thermogravimetric analysis (TGA, l81-II, LINSEIS) and differential scanning calorimeter (DSC) were performed.

[0088] <Production of cyclosilazane compounds> [Example 1] 2,2,5,5-Tetrafluoro-1-isopropyl-[1,2,5]azadisilacyclopentane Step 1: Synthesis of 1,2-bis(trichlorosilyl)ethane [ka]

[0089] Under an anhydrous and inert atmosphere, a flame-dried 1 L flask was equipped with a reflux apparatus and charged with 310 g (2.29 mol) of trichlorosilane and 0.1 g (0.2 mmol) of chloroplatinic acid (HPtCl6·6H2O). The flask was then heated to 70 °C. 351.1 g (2.17 mol) of trichlorovinylsilane was then gradually added, and the mixture was stirred for 2 hours to complete the reaction. The reaction mixture was distilled under reduced pressure at 80 °C and 1.5 torr to obtain 630 g (98% yield, 2.12 mol) of 1,2-bis(trichlorosilyl)ethane.

[0090] 1 H NMR(C6D6): 1.04ppm (s, 4H, Si-CH2-CH2-Si)

[0091] Step 2: Synthesis of 2,2,5,5-Tetrachloro-1-isopropyl-[1,2,5]azadisilacyclopentane [ka]

[0092] Under an anhydrous and inert atmosphere, a flame-dried 5 L flask was charged with 630 g (2.12 mol) of 1,2-bis(trichlorosilyl)ethane synthesized in Step 1 and 548 g (6.36 mol) of n-hexane, cooled to below -30°C, and 3120 ml (5.3 mol) of 1.7 M tert-butyl lithium was slowly added. After the addition was completed, the temperature was gradually raised to below 0°C and stirred for 1 hour, after which 150 g (2.55 mol) of isopropylamine was slowly added. During the addition, the neon temperature was maintained below 15°C. After the addition was completed, the temperature was gradually raised to room temperature and stirred for 2 hours to complete the reaction. The reaction mixture was filtered, and the filtrate was distilled under reduced pressure at 50°C and 0.8 torr to obtain 176 g (0.62 mol) of 2,2,5,5-tetrachloro-1-isopropyl-[1,2,5]azadisilacyclopentane (29% yield, 93.9% GC purity).

[0093] 1 H NMR (C6D6): 0.88ppm (s, 4H, Si-CH2-CH2-Si), 1.26ppm (d, 6H, N-CH(CH3)2), 3.58ppm (m, 1H N-CH(CH3)2),

[0094] Step 3: 2,2,5,5-Tetrafluoro-1-isopropyl-[1,2,5]azadisilacyclopentane ) synthesis [ka]

[0095] In an anhydrous and inert atmosphere, 250 g (1.87 mol) of diethylene glycol dimethyl ether and 96.91 g (3.74 mol) of lithium fluoride were placed in a flame-dried 1 L flask and heated to 60 °C, followed by the gradual addition of 176 g (0.62 mol) of 2,2,5,5-Tetrachloro-1-isopropyl-[1,2,5]azadisilacyclopentane synthesized in Step 2. After the addition was complete, the mixture was heated to 65 °C and stirred for 12 hours to complete the reaction. The reaction mixture was filtered, and the filtrate was distilled under reduced pressure at 74°C and 116.5 torr to obtain 54 g (0.62 mol) of 2,2,5,5-tetrafluoro-1-isopropyl-[1,2,5]azadisilacyclopentane (yield 40%, GC purity 97.6%).

[0096] 1 H NMR (C6D6): 0.90ppm (s, 4H, Si-CH2-CH2-Si), 1.26ppm (d, 6H, N-CH(CH3)2), 3.58ppm (m, 1H, N-CH(CH3)2), 13 C NMR (C6D6): 0.49ppm, 25.5ppm, 45.3ppm 29 Si NMR (in C6D6): -31.2ppm (t, 2Si)

[0097] Figure 1 shows the thermogravimetric (TGA) and differential scanning calorimetry (DSC) analysis results for 2,2,5,5-tetrafluoro-1-isopropyl-[1,2,5]azadisilacyclopentane prepared in Example 1. Referring to Figure 1, it can be seen that the compound of Example 1 has a single evaporation step at about 150°C, leaving almost no residue at 150°C, demonstrating rapid evaporation characteristics. Furthermore, referring to the DSC graph in Figure 1, it can be seen that thermal decomposition of the compound begins at about 250°C, indicating that the compound of Example 1 has excellent thermal stability and volatility.

[0098] As described above, the present invention has been described using specific matters and limited examples and comparative examples, but these are provided to facilitate a more general understanding of the present invention, and the present invention is not limited to the above examples. A person having ordinary skill in the art to which the present invention pertains can make various modifications and variations from such descriptions.

[0099] Therefore, the concept of the present invention should not be limited to the above-described embodiments, and it can be said that not only the scope of the claims described below, but also all modifications that are equivalent to or equivalent to the scope of the claims fall within the scope of the concept of the present invention.

Claims

1. A cyclosilazane compound represented by the following chemical formula 1. [Chemical formula 1] 【Chemical 1】 (In the above Chemical Formula 1, X is a halogen; R １ ~R ３ are each independently hydrogen, halogen, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; R ４ is hydrogen, halogen, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, or —Si(R １１ ) (R １２ ) (R １３ ) and A is -(CR ７ R ８ ) ｎ - and R ５ ~R ８ and R １１ ~R １３ are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; n is an integer from 1 to 5.

2. The X is fluoro, and R １ ~R ３ are each independently hydrogen, fluoro, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl, and R ４ is hydrogen, fluoro, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or —Si(R １１ ) (R １２ ) (R １３ ) and A is -(CR ７ R ８ ) ｎ - and R ５ ~R ８ and R １１ ~R １３ are each independently hydrogen, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl, and n is an integer of 1 to 3.

3. The cyclosilazane compound according to claim 1, represented by the following chemical formula 2: [Chemical formula 2] 【Chemistry 2】 (In the above chemical formula 2, R １ ~R ３ are each independently hydrogen, fluoro, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; R ４ is hydrogen, fluoro, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, or —Si(R １１ ) (R １２ ) (R １３ ) and R １１ ~R １３ are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; n is an integer from 1 to 5.

4. The R １ ~R ３ are each independently hydrogen, fluoro, or C1-C4 alkyl; R ４ is hydrogen, fluoro, C1-C4 alkyl or —Si(R １１ ) (R １２ ) (R １３ ) and R １１ ~R １３ are each independently hydrogen or C1-C4 alkyl; 4. The cyclosilazane compound according to claim 3, wherein n is an integer of 1 to 3.

5. The cyclosilazane compound according to claim 1, represented by the following chemical formula 3: [Chemical formula 3] 【Chemistry 3】 (In the above chemical formula 3, R １ and R ３ are each independently hydrogen, fluoro, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; R ４ is hydrogen, fluoro, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, or —Si(R １１ ) (R １２ ) (R １３ ) and R １１ ~R １３ are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl, or C2-C7 alkynyl; n is an integer from 1 to 5.

6. The R １ and R ３ are each independently hydrogen, fluoro, or C1-C4 alkyl; R ４ is hydrogen, fluoro, C1-C4 alkyl or —Si(R １１ ) (R １２ ) (R １３ ) and R １１ ~R １３ are each independently hydrogen or C1-C4 alkyl; 6. The cyclosilazane compound according to claim 5, wherein n is an integer of 1 to 3.

7. 2. The cyclosilazane compound of claim 1, selected from the following structures: 【Chemistry 4】

8. A composition for depositing a silicon-containing thin film, comprising the cyclosilazane compound according to any one of claims 1 to 7.

9. A method for producing a silicon-containing thin film using a cyclosilazane compound represented by the following chemical formula 1 or a composition for depositing a silicon-containing thin film containing the same: [Chemical formula 1] 【Chemistry 5】 (In the above Chemical Formula 1, R １ ~R ６ , X and A are defined as in claim 1.

10. The method for producing a silicon-containing thin film according to claim 9 , 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 silicon-containing thin film contains 0.5 at % or more of fluorine.

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