Cyclosilazane compound and method for preparing silicon-containing thin film using same

Abstract

The present invention relates to a cyclosilazane compound, a composition for depositing a silicon-containing thin film comprising the same, and a method for preparing a silicon-containing thin film using the same, the silicon-containing thin film prepared using the cyclosilazane compound as a silicon precursor according to the present invention not only has excellent chemical stability and thermal stability, but also has a low dielectric constant, therefore, the present invention can be effectively used as an insulating film for a semiconductor device, in particular, as a spacer for a semiconductor micronization process.

Description

Technical Field

[0001] The present invention relates to a cyclosilazane compound used as a precursor of a low-dielectric silicon-containing film, a composition for depositing a silicon-containing film containing the cyclosilazane compound, and a method for preparing a silicon-containing film using the cyclosilazane compound. Background Art

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

[0003] On the other hand, it is very important for the insulating film used as spacer in semiconductor devices to have a low dielectric constant and excellent etching resistance. In addition, in order to be applied to actual processes, conditions such as simple process, excellent chemical stability and thermal stability must be met. Therefore, the requirements for the physical properties of the insulating film used as spacer for next-generation semiconductor devices are becoming increasingly higher.

[0004] To this end, research continues to lower the dielectric constant of silicon thin films. However, there are challenges with achieving a sufficiently low dielectric constant, reducing thermal stability and etching resistance, and lowering productivity due to slow film formation speeds. Furthermore, as a solution to simultaneously achieve both a low dielectric constant and etching resistance in silicon thin films, fluorine (F) doping has been proposed after the silicon-containing film is formed. However, this requires an additional fluorine doping step, complicating the process. Furthermore, doping primarily occurs near the film surface, making it difficult to perform fluorine doping deeper than the surface. Consequently, this poses limitations, such as reduced film quality.

[0005] Prior art literature

[0006] Patent Literature

[0007] (Patent Document 1) Korean Patent Publication No. 10-2002-0063196 (August 1, 2002) Summary of the Invention

[0008] Problems to be solved by the invention

[0009] One aspect of the present invention provides a cyclosilazane compound as a precursor for a high-quality low-dielectric silicon-containing film and a composition for depositing a silicon-containing film comprising the same.

[0010] Another aspect of the present invention provides a method for preparing a silicon-containing thin film, which can deposit a thin film at a high film deposition rate even under mild conditions and can prepare a high-quality thin film with a high yield.

[0011] Means used to solve problems

[0012] One aspect of the present invention provides a cyclosilazane compound represented by the following Chemical Formula 1.

[0013] [Chemical Formula 1]

[0014]

[0015] (In the chemical formula 1,

[0016] X is a halogen;

[0017] R1 to R3 are each independently hydrogen, halogen, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl;

[0018] R4 is hydrogen, halogen, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl or -Si(R 11 )(R 12 )(R 13 );

[0019] A is -(CR7R8) n -;

[0020] R5 to R8 and R 11 to R 13 are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl;

[0021] n is an integer from 1 to 5.)

[0022] The X may be fluorine; R1 to R3 may each independently be hydrogen, fluorine, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; R4 may be hydrogen, fluorine, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl or -Si(R 11 )(R 12 )(R 13 ); A can be -(CR7R8) n -; R5 to R8 and R 11 to R 13 Each independently may be hydrogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; n may be an integer from 1 to 3.

[0023] The cyclic silazane compound according to one aspect may be represented by the following Chemical Formula 2.

[0024] [Chemical Formula 2]

[0025]

[0026] (In the chemical formula 2,

[0027] R1 to R3 are each independently hydrogen, fluorine, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl;

[0028] R4 is hydrogen, fluorine, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl or -Si(R 11 )(R 12 )(R 13 );

[0029] R 11 to R 13 are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl;

[0030] n is an integer from 1 to 5.)

[0031] Said R1 to R3 may be each independently hydrogen, fluorine or C1-C4 alkyl; R4 may be hydrogen, fluorine, C1-C4 alkyl or -Si(R 11 )(R 12 )(R 13 );R 11 to R 13 Each independently may be hydrogen or a C1-C4 alkyl group; and n may be an integer from 1 to 3.

[0032] The cyclic silazane compound according to one aspect may be represented by the following Chemical Formula 3.

[0033] [Chemical Formula 3]

[0034]

[0035] (In the chemical formula 3,

[0036] R1 and R3 are each independently hydrogen, fluorine, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl;

[0037] R4 is hydrogen, fluorine, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl or -Si(R 11 )(R 12 )(R 13 );

[0038] R 11 to R 13 are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl;

[0039] n is an integer from 1 to 5.)

[0040] Said R1 and R3 can each independently be hydrogen, fluorine or C1-C4 alkyl; R4 is hydrogen, fluorine, C1-C4 alkyl or -Si(R 11 )(R 12 )(R 13 );R 11 to R 13 Each independently may be hydrogen or a C1-C4 alkyl group; and n may be an integer from 1 to 3.

[0041] The cyclosilazane compound according to one aspect may be selected from the following structures.

[0042]

[0043] Yet another aspect of the present invention provides a composition for depositing a silicon-containing thin film, comprising a cyclosilazane compound.

[0044] Another aspect of the present invention provides a method for preparing 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 comprising the cyclosilazane compound.

[0045] [Chemical Formula 1]

[0046]

[0047] (In the chemical formula 1,

[0048] R1 to R6, X and A are the same as defined above.)

[0049] The silicon-containing film may be a film containing fluorine and silicon.

[0050] The silicon-containing thin film may contain 0.5 at % or more of fluorine.

[0051] Effects of the Invention

[0052] The cyclosilazane compound according to one aspect of the present invention has very excellent thermal stability, can deposit thin films at a high film deposition rate even under low temperature conditions, and can prepare high-quality silicon-containing thin films with high purity through a simple preparation process.

[0053] Furthermore, a silicon-containing film prepared from a cyclosilazane compound according to one aspect has not only excellent chemical and thermal stability but also a very low dielectric constant, and is therefore expected to be effectively used as an insulating film for semiconductor devices, and in particular, can be effectively used as a spacer in a semiconductor scaling process. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 These are the results of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analysis of 2,2,5,5-tetrafluoro-1-isopropyl-[1,2,5]azasilane prepared in Example 1. DETAILED DESCRIPTION

[0055] Unless otherwise defined in this specification, all technical terms and scientific terms have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. The terms used in this specification are only for the purpose of effectively describing specific embodiments and are not intended to limit the present invention.

[0056] Unless otherwise indicated in the context, the singular forms used in this specification may be intended to include the plural forms as well.

[0057] Throughout this specification, unless otherwise specifically stated, “comprising,” “having,” “containing,” or “having” a certain constituent element does not exclude other constituent elements, but means that other constituent elements may also be included and does not exclude elements, materials, or processes that are not listed.

[0058] The numerical ranges used in this specification include: lower and upper limits and all values ​​within the range; increments logically derived based on the form and magnitude of the defined range; all values ​​that are doubly defined; and all possible combinations of upper and lower limits within the numerical range defined in different forms. In this specification, unless otherwise specified, values ​​outside the numerical range that may appear due to experimental errors or rounding of values ​​are also included in the defined numerical range.

[0059] In this specification, unless otherwise defined, "about" may be considered to be a value within 30%, 25%, 20%, 15%, 10%, or 5% of a specified value.

[0060] The term "alkyl" as used herein is an organic radical derived from an aliphatic hydrocarbon by removing a hydrogen atom, and may include a straight or branched chain alkyl group. The alkyl group may have 1 to 7 carbon atoms, specifically 1 to 5 carbon atoms, specifically 1 to 4 carbon atoms. As an example, the straight chain alkyl group includes a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, and a n-heptyl group, and the branched chain alkyl group includes an isopropyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a 2-methylhexyl group, a 3-methylbutyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 4-methylhexyl group, a 5-methylhexyl group, a 2,3-dimethylbutyl group, a 2,3-dimethylpentyl group, a 2,4-dimethylpentyl group, etc., but is not limited thereto.

[0061] The terms used in this specification include "alkenyl" and "alkynyl" which are linear or branched unsaturated hydrocarbon groups containing one or more double bonds, and "alkenyl" and "alkynyl" which are linear or branched unsaturated hydrocarbon groups containing one or more triple bonds.

[0062] Hereinafter, the present invention will be described in detail. However, this is only exemplary, and the present invention is not limited to the specific embodiments described in the exemplary embodiments.

[0063] One aspect of the present invention provides a cyclosilazane compound useful as a precursor for high-quality, low-dielectric silicon-containing films.

[0064] Specifically, the cyclosilazane compound according to one aspect may be represented by Chemical Formula 1 below.

[0065] [Chemical Formula 1]

[0066]

[0067] (In the chemical formula 1,

[0068] X is a halogen;

[0069] R1 to R3 are each independently hydrogen, halogen, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl;

[0070] R4 is hydrogen, halogen, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl or -Si(R 11 )(R 12 )(R 13 );

[0071] A is -(CR7R8) n -;

[0072] R5 to R8 and R 11 to R 13 are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl;

[0073] n is an integer of 1 to 5. If n is an integer greater than 2, R7 and R8 may be different from each other.

[0074] According to one aspect, the cyclosilazane compound has the structural features of Chemical Formula 1, for example, a cyclic structure containing a disilazane group (*-Si-N-Si-*) and one or more halogen (F, Cl, Br, I) substituents. Therefore, a low dielectric film can be provided. The cyclosilazane compound exists in a liquid state at room temperature and has excellent volatility and thermal stability. Even under low temperature conditions, a thin film can be deposited at a high film deposition rate and has high purity and excellent durability.

[0075] As an example, the X may be fluorine (—F).

[0076] As an example, R1 to R3 may each independently be hydrogen, fluorine, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; R4 may be hydrogen, fluorine, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl or -Si(R 11 )(R 12 )(R 13 ); A can be -(CR7R8) n -; R5 to R8 and R 11 to R 13 Each independently may be hydrogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; and n may be an integer from 1 to 3.

[0077] Specifically, the cyclosilazane compound according to one aspect may be represented by Chemical Formula 2 below.

[0078] [Chemical Formula 2]

[0079]

[0080] (In the chemical formula 2,

[0081] R1 to R3 are each independently hydrogen, fluorine, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl;

[0082] R4 is hydrogen, fluorine, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl or -Si(R 11 )(R 12 )(R 13 );

[0083] R 11 to R 13 are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl;

[0084] n is an integer from 1 to 5.)

[0085] As an example, R1 to R3 may be independently hydrogen, fluorine or C1-C4 alkyl; R4 may be hydrogen, fluorine, C1-C4 alkyl or -Si(R 11 )(R 12 )(R 13 );R 11 to R 13 Each independently may be hydrogen or a C1-C4 alkyl group; and n may be an integer from 1 to 3.

[0086] Specifically, the cyclosilazane compound according to one aspect may be represented by the following Chemical Formula 3.

[0087] [Chemical Formula 3]

[0088]

[0089] (In the chemical formula 3,

[0090] R1 and R3 are each independently hydrogen, fluorine, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl;

[0091] R4 is hydrogen, fluorine, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl or -Si(R 11 )(R 12 )(R 13 );

[0092] R 11 to R 13 are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl;

[0093] n is an integer from 1 to 5.)

[0094] As an example, in the chemical formula 3, the R1 and R3 may be each independently hydrogen, fluorine or C1-C4 alkyl; R4 may be hydrogen, fluorine, C1-C4 alkyl or -Si(R 11 )(R 12 )(R 13 );R 11 to R 13 Each independently may be hydrogen or a C1-C4 alkyl group; and n may be an integer from 1 to 3.

[0095] As an example, R1 and R3 can each independently be hydrogen, fluorine or methyl.

[0096] As an example, the R1 and R3 may be the same and may be hydrogen, fluorine, C1-C4 alkyl or methyl.

[0097] As an example, R4 can be hydrogen, fluorine, C1-C4 alkyl or -Si(R 11 )(R 12 )(R 13 );R 11 to R 13 Each independently may be hydrogen or a C1-C4 alkyl group; and n may be an integer from 1 to 3.

[0098] As an example, the R 11 to R 13 can be the same and can be hydrogen or C1-C4 alkyl or methyl.

[0099] As an example, the R4 can be hydrogen, fluorine, branched (C3-C7) alkyl or -Si(R 11 )(R 12 )(R 13 ), for example, the branched (C3-C7) alkyl group may be isopropyl, sec-butyl, isobutyl, tert-butyl or isopentyl.

[0100] As an example, n may be 1 or 2.

[0101] The cyclosilazane compound according to one aspect may be selected from the following structures, but is not limited thereto.

[0102]

[0103] Hereinafter, a method for preparing the cyclosilazane compound represented by Chemical Formula 1 according to one aspect will be specifically described. However, it is apparent that the compound can also be synthesized by other methods recognized by those skilled in the art. Furthermore, the organic solvent used is not limited, and the reaction time and temperature can of course be varied without departing from the core of the invention.

[0104] According to one aspect, a method for preparing the cyclosilazane compound represented by Chemical Formula 1 may include step (A): reacting a compound represented by the following Chemical Formula 11 and a compound represented by Chemical Formula 12.

[0105] [Chemical Formula 11]

[0106]

[0107] [Chemical Formula 12]

[0108] R4-NH2

[0109] (In the chemical formulas 11 and 12,

[0110] Y1 and Y2 are each independently Cl or Br;

[0111] R1 to R6, X and A are the same as those defined in Chemical Formula 1.

[0112] In addition, the method for preparing the cyclosilazane compound represented by Chemical Formula 1 according to one aspect may further include a step (B) of reacting a fluorine source after the step (A).

[0113] The step (A) can be carried out at a temperature of 0°C to 30°C for 1 to 10 hours, specifically, at a temperature of 10°C to 30°C for 1 to 5 hours, but is not limited thereto and can be varied according to the type and amount of reactants and solvents used.

[0114] The fluorine source can be selected from alkali metal fluorides such as LiF, KF, NaF, RbF, CsF, or transition metal fluorides such as AgF, AgF2, ZnF2, CuF2, CuF2·H2O, NiF2, SnF2, InF3, ScF3, TiF3, MnF3, CoF3, CrF3, AuF3, FeF3, MnF3, BiF3, SbF3, but is not limited thereto.

[0115] In addition, the step (B) can be carried out at a temperature of 30°C to 70°C for 5 to 20 hours, specifically, at a temperature of 40°C to 60°C for 10 to 20 hours, but is not limited thereto and can be changed according to the type and amount of the reactants and solvents used.

[0116] Another aspect of the present invention provides a composition for depositing a silicon-containing thin film, comprising the cyclosilazane compound.

[0117] According to one aspect, a composition for depositing a silicon-containing thin film includes a cyclosilazane compound represented by Chemical Formula 1 as a precursor for depositing the thin film. 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 based on considerations of film formation conditions, thickness of the thin film, properties of the thin film, and application of the thin film.

[0118] Another aspect of the present invention provides a method for preparing 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 comprising the cyclosilazane compound.

[0119] [Chemical Formula 1]

[0120]

[0121] (In the chemical formula 1,

[0122] R1 to R6, X and A are the same as those defined in Chemical Formula 1.

[0123] According to one aspect of the method for preparing a silicon-containing thin film, a high-quality silicon-containing thin film can be prepared at a high deposition rate even at low temperature and low power by using the cyclosilazane compound represented by Chemical Formula 1 as a precursor.

[0124] Specifically, the silicon-containing film according to one aspect may be a fluorine- and silicon-containing film. In the method for preparing a silicon-containing film according to one aspect, if the cyclosilazane compound represented by Chemical Formula 1 contains fluorine (F), the fluorine (F) of the cyclosilazane compound remains in the film, thereby providing a low-dielectric-constant, high-quality fluorine- and silicon-containing film.

[0125] Specifically, according to one aspect, the silicon-containing film may contain fluorine at more than 0.5 at%, or more than 1.0 at%, or more than 1.5 at%, or more than 2.0 at%, or more than 2.5 at%, or less than 10 at%, or less than 9 at%, or less than 8 at%, or less than 7 at%.

[0126] According to one aspect, a cyclosilazane compound has the advantage of being able to prepare a thin film containing both fluorine and silicon using a single precursor. Specifically, a thin film containing fluorine and silicon is typically doped with fluorine using a fluorine-containing precursor after the silicon-containing film is prepared. This disadvantageously results in an uneven fluorine content within the film. In contrast, the method for preparing a silicon-containing thin film of the present invention overcomes this disadvantage, enabling the preparation of a fluorine-containing and silicon thin film having a uniform fluorine content using a single precursor.

[0127] In the method for preparing a silicon-containing thin film according to one aspect, the cyclosilazane compound and the reaction gas may be supplied organically or independently. In addition, the cyclosilazane compound and the reaction gas may be supplied continuously or discontinuously, and the discontinuous supply may include a pulse form.

[0128] As an example, the method for preparing the silicon-containing thin film may include:

[0129] Step a), maintaining the temperature of the substrate installed in the chamber above 100° C.;

[0130] Step b), adsorbing the cyclosilazane compound represented by Chemical Formula 1 or a composition for depositing a silicon-containing thin film comprising the cyclosilazane compound onto a substrate; and

[0131] Step c) injecting a reaction gas into the substrate on which the cyclosilazane compound or the composition for depositing a silicon-containing thin film containing the cyclosilazane compound is adsorbed, so as to deposit a silicon-containing thin film.

[0132] Specifically, the method for preparing the silicon-containing thin film may include:

[0133] Step a), maintaining the temperature of the substrate installed in the chamber above 100° C.;

[0134] Step b), adsorbing the cyclosilazane compound represented by Chemical Formula 1 or a composition for depositing a silicon-containing thin film comprising the cyclosilazane compound onto a substrate; and

[0135] Step c), purging the residual cyclosilazane compound or the residual composition for thin film deposition and by-products;

[0136] Step d), injecting a reaction gas into the substrate adsorbed with the cyclosilazane compound or the composition for thin film deposition containing the cyclosilazane compound to form a silicon-containing thin film; and

[0137] Step e) purging the remaining reaction gas and by-products.

[0138] In addition, as an example, the method for preparing the silicon-containing thin film may include:

[0139] maintaining the temperature of the substrate mounted in the chamber at 100° C. or higher; and

[0140] A step of simultaneously injecting the cyclosilazane compound represented by Chemical Formula 1 or a composition for depositing a silicon-containing thin film containing the cyclosilazane compound and a reaction gas to deposit a silicon-containing thin film.

[0141] The deposition method is not particularly limited as long as it is commonly used in the field. For example, 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) or plasma enhanced atomic layer deposition (PEALD) can be used, but are not limited thereto.

[0142] The type of the reaction gas is not particularly limited as long as it is commonly used in the field. As an example, it can 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), acetic anhydride ((CH3CO)2O), or a combination thereof. The gas used for purge can be nitrogen (N2), argon (Ar), helium (He), or a combination thereof.

[0143] The substrate is not particularly limited as long as it is commonly used in the field. For example, it can be a substrate containing one or more semiconductor materials of Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs and InP; a silicon on insulator (SOI) substrate; a quartz substrate; or a glass substrate for display; a flexible plastic substrate of polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES), polyester (PE), etc.

[0144] In addition, in addition to forming a thin film directly on the substrate, the silicon-containing thin film may also form a plurality of conductive layers, dielectric layers, or insulating layers between the substrate and the silicon-containing thin film.

[0145] As an example, specifically, the temperature of the substrate can be adjusted to 100°C to 1000°C, or 300°C to 1000°C, or 500°C to 1000°C. Under the temperature conditions, the fluorine (F) of the cyclosilazane compound represented by Chemical Formula 1 can remain in the film, and a high-quality fluorine-and-silicon-containing film can be provided, and a film with a lower dielectric constant can be provided.

[0146] As an example, the reaction gas may be supplied after generating and activating plasma of 50 W to 1000 W, or 100 W to 800 W, or 400 W to 600 W.

[0147] That is, according to one aspect of the method for preparing a silicon-containing thin film, the compound of Chemical Formula 1 is used as a precursor, so that the thin film can be efficiently prepared even under low temperature and low plasma generation.

[0148] In addition, one aspect of the present invention provides a silicon-containing thin film prepared by the preparation method.

[0149] According to one aspect, the silicon-containing film can be any film that can be prepared within the scope recognized by ordinary technicians in the technical field. Specifically, it can be a fluorinated silicon carbide film, a fluorinated silicon oxide film, a fluorinated silicon film, a silicon carbide film, etc. In addition, various high-quality silicon-containing films can be prepared within the scope recognized by ordinary technicians in this field.

[0150] According to one aspect, the silicon-containing film not only has excellent chemical stability and thermal stability, but also has a very low dielectric constant, and can therefore be used for a variety of purposes, for example, as an insulating film, diffusion barrier film, spacer, dielectric material between metals, and protective film layer when preparing electronic devices.

[0151] The above embodiments will be described in more detail below by way of examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the claims.

[0152] The physical properties of the examples were measured as follows.

[0153] 1) Thermal characteristics

[0154] In order to measure the thermal stability, volatility and decomposition temperature of the cyclosilazane compounds, thermogravimetric analysis (TGA, thermogravimetric analyzer model: L81-II, manufacturer: LINSEIS, Germany) and differential scanning calorimetry (DSC) analysis were performed.

[0155] Preparation of cyclosilazane compounds

[0156] [Example 1]

[0157] 2,2,5,5-Tetrafluoro-1-isopropyl-[1,2,5]azadisilacyclopentane

[0158] Step 1: Synthesis of 1,2-bis(trichlorosilyl)ethane

[0159]

[0160] Under an anhydrous inert atmosphere, a flame-dried 1L flask was set up with a reflux system, and 310g (2.29mol) of trichlorosilane and 0.1g (0.2mmol) of chloroplatinic acid hexahydrate (HPtCl6·6H2O) were added, followed by heating to 70°C. 351.1g (2.17mol) of trichlorovinylsilane was slowly added, followed by stirring for 2 hours to complete the reaction. The reaction mixture was distilled under reduced pressure (80°C, 1.5 torr) to obtain 630g (2.12mol) of 1,2-bis(trichlorosilyl)ethane (yield 98%).

[0161] 1 H NMR (C6D6): 1.04ppm (s, 4H, Si-CH2-CH2-Si)

[0162] Step 2: Synthesis of 2,2,5,5-Tetrachloro-1-isopropyl-[1,2,5]azadisilacyclopentane

[0163]

[0164] Under an anhydrous inert atmosphere, add 630g (2.12mol) of 1,2-bis(trichlorosilyl)ethane synthesized in step 1 and 548g (6.36mol) of n-hexane to a flame-dried 5L flask, cool to below -30°C, and slowly add 3120mL (5.3mol) of 1.7M tert-butyllithium. After the addition is complete, gradually heat to below 0°C, stir for 1 hour, and then slowly add 150g (2.55mol) of isopropylamine. During the addition, keep the internal temperature below 15°C. After the addition is completed, gradually heat to room temperature and stir for 2 hours to complete the reaction. After filtering the reaction mixture, the filtrate was distilled under reduced pressure (50° C., 0.8 torr) to obtain 176 g (0.62 mol) of 2,2,5,5-tetrachloro-1-isopropyl-[1,2,5]azadisilacyclopentane (yield 29%, GC purity 93.9%).

[0165] 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)

[0166] Step 3: Synthesis of 2,2,5,5-Tetrafluoro-1-isopropyl-[1,2,5]azadisilacyclopentane

[0167]

[0168] Under an anhydrous inert atmosphere, add 250 g (1.87 mol) of diethylene glycol dimethyl ether and 96.91 g (3.74 mol) of lithium fluoride to a flame-dried 1L flask. After heating to 60°C, slowly add 176 g (0.62 mol) of 2,2,5,5-tetrachloro-1-isopropyl-[1,2,5]azadisilacyclopentane (synthesized in Step 2). After the addition is complete, stir at 65°C for 12 hours to complete the reaction. After filtering the reaction mixture, the filtrate was distilled under reduced pressure (74° C., 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%).

[0169] 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)

[0170] 13 C NMR (C6D6): 0.49ppm, 25.5ppm, 45.3ppm

[0171] 29 Si NMR (in C6D6): -31.2ppm (t, 2Si).

[0172] Figure 1 The results of thermogravimetric (TGA) and differential scanning calorimetry (DSC) analysis of 2,2,5,5,-tetrafluoro-1-isopropyl-[1,2,5]azadisilacyclopentane prepared in Example 1 are shown. Figure 1 It can be seen that the compound of Example 1 has a single evaporation step at a temperature of about 150°C, and there is almost no residual mass at a temperature of 150°C, showing a rapid vaporization feature. Figure 1 From the DSC graph, it can be seen that the thermal decomposition of the compound begins after the temperature reaches about 250° C., and it can be seen that the compound of Example 1 has very excellent thermal stability and excellent volatility.

[0173] As described above, in the present invention, specific matters and limited embodiments and comparative examples are described, but this is only provided to help a more comprehensive understanding of the present invention. The present invention is not limited to the above-mentioned embodiments, and any person skilled in the art in the field to which the present invention belongs can make various modifications and variations based on these descriptions.

[0174] Therefore, the idea of ​​the present invention should not be limited to the illustrated embodiments, and it can be said that not only the scope of the claims set forth below but also all modifications equivalent to or equivalent to the scope of the claims belong to the scope of the idea of ​​the present invention.

Claims

1. A cyclosilazane compound, wherein The cyclic silazane compound is represented by the following chemical formula 1: [Chemical Formula 1] In the 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 ); A is -(CR7R8) n -; R5 to R8 and R 11 to R 13 are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl; n is an integer of 1 to 5.

2. The cyclosilazane compound according to claim 1, wherein Said X is fluorine; R1 to R3 are each independently hydrogen, fluorine, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; R4 is hydrogen, fluorine, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl or -Si(R 11 )(R 12 )(R 13 ); A is -(CR7R8) n -; R5 to R8 and R 11 to R 13 are each independently hydrogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; n is an integer of 1 to 3.

3. The cyclosilazane compound according to claim 1, wherein The cyclic silazane compound is represented by the following chemical formula 2: [Chemical Formula 2] In the chemical formula 2, R1 to R3 are each independently hydrogen, fluorine, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl; R4 is hydrogen, fluorine, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl or -Si(R 11 )(R 12 )(R 13 ); R 11 to R 13 are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl; n is an integer of 1 to 5.

4. The cyclosilazane compound according to claim 3, wherein R1 to R3 are each independently hydrogen, fluorine or C1-C4 alkyl; R4 is hydrogen, fluorine, C1-C4 alkyl or -Si(R 11 )(R 12 )(R 13 ); R 11 to R 13 Each is independently hydrogen or C1-C4 alkyl; n is an integer of 1 to 3.

5. The cyclosilazane compound according to claim 1, wherein The cyclic silazane compound is represented by the following chemical formula 3: [Chemical Formula 3] In the chemical formula 3, R1 and R3 are each independently hydrogen, fluorine, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl; R4 is hydrogen, fluorine, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl or -Si(R 11 )(R 12 )(R 13 ); R 11 to R 13 are each independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl or C2-C7 alkynyl; n is an integer of 1 to 5.

6. The cyclosilazane compound according to claim 5, wherein Said R1 and R3 are each independently hydrogen, fluorine or C1-C4 alkyl; R4 is hydrogen, fluorine, C1-C4 alkyl or -Si(R 11 )(R 12 )(R 13 ); R 11 to R 13 Each is independently hydrogen or C1-C4 alkyl; n is an integer of 1 to 3.

7. The cyclosilazane compound according to claim 1, wherein The cyclosilazane compound is selected from the following structures, 8. A composition for depositing a silicon-containing thin film, wherein: The composition comprises a cyclosilazane compound selected from any one of claims 1 to 7.

9. A method for preparing a silicon-containing thin film, wherein: The method uses a cyclosilazane compound represented by the following Chemical Formula 1 or a composition for depositing a silicon-containing thin film comprising the cyclosilazane compound. [Chemical Formula 1] In the chemical formula 1, R1 to R6, X and A are the same as defined in claim 1.

10. The method for preparing a silicon-containing thin film according to claim 9, wherein: The silicon-containing film is a film containing fluorine and silicon.

11. The method for preparing 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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