Novel silylcyclodisilazane compound and method for producing silicon-containing thin film using the same

Abstract

Provided are a novel silylcyclodisilazane compound, a composition for depositing a silicon-containing film comprising the compound, and a method for manufacturing a silicon-containing film using the same. Since the silylcyclodisilazane compound of the present invention has high reactivity, thermal stability and high volatility, it can be used as a silicon-containing precursor to manufacture high-quality silicon-containing films by various deposition methods.

Description

Technical Field

[0001] The present invention relates to a novel silylcyclodisilazane compound and a silicon-containing thin film formed using the same, and more particularly to a novel silylcyclodisilazane compound which is thermally stable and highly volatile and is in a liquid form at room temperature and an easily operable pressure, and a method for producing a silicon-containing thin film using the same. Background Art

[0002] In the semiconductor field, silicon-containing thin films in several forms, such as silicon films, silicon oxide films, silicon nitride films, silicon carbonitride films, and silicon oxynitride films, are manufactured by various deposition processes and applied in various fields.

[0003] In particular, silicon oxide films and silicon nitride films are used as insulating films, diffusion barrier films, hard masks, etching barrier layers, seed layers, spacers, trench isolation, intermetallic dielectric materials, and protective film layers in the manufacture of devices due to their excellent barrier properties and oxidation resistance. Recently, polycrystalline silicon films have been used in thin film transistors (TFTs), solar cells, etc., and have been gradually applied to various fields.

[0004] Well-known representative technologies for manufacturing silicon-containing thin films include metal organic chemical vapor deposition (MOCVD), which is used to form a film on a substrate surface by a reaction between a silicon precursor in the form of a mixed gas and a reactive gas, or to form a film by a direct reaction of a silicon precursor in the form of a mixed gas on the substrate surface; and atomic layer deposition (ALD), which is used to form a film by physically or chemically adsorbing a silicon precursor in the form of a gas onto a substrate surface, and then sequentially injecting reactive gases; and various technologies for manufacturing thin films, such as low pressure chemical vapor deposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD) using plasma capable of deposition at low temperatures, and plasma enhanced atomic layer deposition (PEALD), which are all technologies applying LPCVD and PECVD, have been applied in the process of manufacturing next-generation semiconductors and display elements, and have been used to form ultra-fine patterns and deposit ultra-thin films with uniform and excellent properties at nanometer-level thickness.

[0005] The generally required characteristics of the precursors used to form silicon-containing films are as follows: ① a compound that is in liquid form at room temperature and normal pressure, and a compound with excellent volatility, ② a compound with excellent reactivity due to its own high thermal stability and low activation energy, ③ a compound that does not produce non-volatile by-products during the process of forming the film, and ④ a compound that is easy to handle, transport and store.

[0006] Representative precursors for forming silicon-containing films are compounds in the form of silanes, chlorosilanes, aminosilanes and alkoxysilanes, and specific examples of these compounds include compounds in the form of chlorosilanes such as dichlorosilane (SiH2Cl2) and hexachlorodisilane (Cl3SiSiCl3), trisilylamine (N(SiH3)3), bisdiethylaminosilane (H2Si(N(CH2CH3)2)2) and diisopropylaminosilane (H3SiN(i-C3H7)2), etc., which are used in large-scale production processes for semiconductor manufacturing and display manufacturing.

[0007] However, due to the miniaturization of components and the increase in aspect ratio, due to the ultra-high integration of components and the diversification of component materials, a technology for forming an ultra-fine film with a uniform thin thickness and excellent electrical characteristics at a desired low temperature has been required. Therefore, high-temperature processes at 600°C or higher using existing silicon precursors, step coverage, etching characteristics, and physical and electrical characteristics of the film have become problems.

[0008] On the other hand, although ultrafine films with uniform thin thickness and excellent electrical characteristics are formed at low temperatures required for elements, productivity has become a problem due to the low film formation speed. Therefore, it has been required to develop new silicon precursors with improved excellent properties. Summary of the invention

[0009] Technical issues

[0010] The object of the present invention is to provide novel silylcyclodisilazane compounds.

[0011] Another object of the present invention is to provide a silylcyclodisilazane compound as a silicon precursor having excellent cohesion at low temperatures due to its high thermal stability and excellent reactivity.

[0012] Another object of the present invention is to provide a composition for depositing a silicon-containing thin film comprising a silylcyclodisilazane compound having high thermal stability and reactivity.

[0013] Another object of the present invention is to provide a method for manufacturing a silicon-containing thin film using the composition for depositing a silicon-containing thin film, which is capable of forming a silicon-containing thin film having excellent physical and electrical characteristics such as a high deposition rate and excellent step coverage.

[0014] Solution to the problem

[0015] The present invention provides novel silylcyclodisilazane compounds which are liquid at room temperature and have high volatility, thermal stability and reactivity.

[0016] In one general aspect, a novel silylcyclodisilazane compound represented by the following Formula 1 is provided:

[0017] [Formula 1]

[0018]

[0019] in

[0020] R 1 To R 6 are each independently hydrogen, C1-C7 alkyl, C3-C7 cycloalkyl or C2-C7 alkenyl; and

[0021] R 7 It is C1-C7 alkyl, C3-C7 cycloalkyl or C2-C7 alkenyl.

[0022] In another general aspect, a composition for depositing a silicon-containing thin film is provided, which includes a silylcyclodisilazane compound having excellent characteristics as a precursor for depositing a thin film and represented by Formula 2 below as a precursor for depositing a silicon-containing thin film.

[0023] [Formula 2]

[0024]

[0025] in

[0026] R 11 To R 17 Each is independently hydrogen, C1-C7 alkyl, C3-C7 cycloalkyl or C2-C7 alkenyl;

[0027] R 18 is hydrogen, C1-C7 alkyl, C3-C7 cycloalkyl, C2-C7 alkenyl or -SiR a R b R c ;as well as

[0028] R a , R b and R c Each is independently hydrogen, C1-C7 alkyl, C3-C7 cycloalkyl or C2-C7 alkenyl;

[0029] The premise is that when R 11 To R 14 When all R 18 Not-SiR a R b R c .

[0030] In another general aspect, a method of manufacturing a silicon-containing thin film using the composition for depositing a silicon-containing thin film according to an exemplary embodiment of the present invention is provided.

[0031] Advantageous Effects of the Invention

[0032] The novel silylcyclodisilazane compound according to the present invention is liquid at room temperature, has high volatility, has excellent thermal stability, and has low activation energy to have excellent reactivity. In addition, the novel silylcyclodisilazane compound according to the present invention exists in a liquid state at room temperature and an operable pressure, and is therefore easy to handle.

[0033] Further, the composition for depositing a silicon-containing thin film according to the present invention includes a silylcyclodisilazane compound having high thermal stability and reactivity, and thus can have excellent physical and electrical properties such as excellent cohesion and excellent step coverage, and minimize the impurity content due to a high deposition rate under various conditions to manufacture a thin film with excellent purity and durability.

[0034] Further, in the method for manufacturing a silicon-containing thin film according to the present invention, by using a composition for depositing a silicon-containing thin film including a silylcyclodisilazane compound to manufacture a silicon-containing thin film, a high-quality silicon-containing thin film having a high silicon content and excellent thermal stability and durability can be manufactured.

[0035] The silicon-containing thin film produced using the silylcyclodisilazane compound according to the present invention as a precursor has high purity and excellent physical and electrical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 Graphs illustrating the results of measuring the vapor pressures of the silylcyclodisilazane compounds prepared in Examples 2 and 4.

[0037] Figure 2 Graphs illustrating the results of thermogravimetric analysis of the silylcyclodisilazane compounds prepared in Examples 2 and 4.

[0038] Figure 3 Graphs showing the results of the deposition rate of the silicon oxide film produced in Example 5.

[0039] Figure 4 1 is a graph showing the results of FT-IR analysis of the silicon oxide film produced in Example 5.

[0040] Figure 5 Graphs showing the results of FT-IR analysis of the silicon nitride film produced in Example 6. DETAILED DESCRIPTION

[0041] Hereinafter, a silylcyclodisilazane compound according to the present invention, a method for producing the same, and a composition for depositing a silicon-containing thin film including the same will be described in detail.

[0042] The "alkyl group" described herein refers to a linear and branched saturated hydrocarbon having 1 to 7 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and includes, for example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl and the like.

[0043] "Halogen" described herein refers to a halogen group element, and includes, for example, fluorine, chlorine, bromine, and iodine.

[0044] The term "alkenyl" described herein, alone or as part of another group, refers to a straight or branched hydrocarbon group having 2 to 7 carbon atoms and one or more carbon-carbon double bonds. Preferred alkenyl groups are lower alkenyl groups having 2 to 5 carbon atoms. More preferred alkenyl groups are groups having 2 to 3 carbon atoms. In addition, alkenyl groups can be substituted at any available point of attachment. Examples of alkenyl groups include vinyl, propenyl, allyl, butenyl and 4-methylbutenyl. The term "alkenyl" includes groups having cis and trans orientations, or alternative E and Z orientations.

[0045] The present invention is to provide a novel silylcyclodisilazane compound which is very useful as a precursor for manufacturing a silicon-containing thin film, and the silylcyclodisilazane compound according to the present invention is represented by the following Formula 1:

[0046] [Formula 1]

[0047]

[0048] in

[0049] R 1 To R 6 are each independently hydrogen, C1-C7 alkyl, C3-C7 cycloalkyl or C2-C7 alkenyl; and

[0050] R 7 It is C1-C7 alkyl, C3-C7 cycloalkyl or C2-C7 alkenyl.

[0051] The silylcyclodisilazane compound according to the present invention has an asymmetric four-membered ring with a Si3N2 molecular skeleton, i.e., an N-silylcyclodisilazane structure, wherein a silyl substituent is introduced into the nitrogen atom of the cyclodisilazane, and at least one hydrogen atom is introduced into the silicon atom of the cyclodisilazane, which has a lower activation energy and a higher thermal stability, and is more reactive as a precursor for depositing a silicon-containing film, and does not produce non-volatile by-products. Therefore, a high-purity silicon-containing film can be easily formed at a high deposition rate. In addition, the silylcyclodisilazane compound has excellent thermal stability, and therefore a film with high durability and excellent purity can be manufactured.

[0052] The silylcyclodisilazane compound according to the present invention is also a compound in a liquid form at room temperature and normal pressure, has excellent volatility, and has a high content of silicon atoms in the molecule, and thus can exhibit an excellent deposition rate.

[0053] Preferably, in Formula 1 of the present invention, R 1 and R 3 can be independently C1-C5 alkyl or C2-C5 alkenyl; R 2 R may be hydrogen, C1-C5 alkyl or C2-C5 alkenyl; 4 It can be a C1-C5 alkyl group or a C2-C5 alkenyl group; R 5 and R 6 may each independently be hydrogen, C1-C5 alkyl or C2-C5 alkenyl; and R 7 It may be a C1-C5 alkyl group or a C2-C5 alkenyl group.

[0054] In order to more effectively use the silylcyclodisilazane compound as a precursor for depositing a thin film, it is more preferred that in Formula 1 of the present invention, R 1 and R 3 can each independently be a C1-C5 alkyl group; R 2 It can be hydrogen or C1-C5 alkyl; R 4 It can be a C1-C5 alkyl group; R 5 and R 6 may each independently be hydrogen or C1-C5 alkyl; and R 7 It can be a C1-C5 alkyl group; more preferably, R 1 and R 3 can each independently be a C1-C3 alkyl group; R 2 It can be hydrogen or C1-C3 alkyl; R 4 It can be a C1-C3 alkyl group; R 5 and R 6 may each independently be hydrogen or C1-C3 alkyl; and R 7It may be a C1-C3 alkyl group, more preferably a C2-C3 alkyl group.

[0055] In a specific example, R 1 and R 3 R may be independently methyl, vinyl, isopropenyl or allyl; 2 R may be hydrogen, methyl, vinyl, isopropenyl or allyl; 4 It can be methyl, vinyl, isopropenyl or allyl; R 5 and R 6 may each independently be hydrogen, methyl, vinyl, isopropenyl or allyl; and R 7 It may be ethyl, vinyl, isopropenyl or allyl.

[0056] In a specific example, the silylcyclodisilazane compound may be at least one selected from the compounds represented by the following Formulae 1-1 to 1-4:

[0057] [Formula 1-1]

[0058]

[0059] [Formula 1-2]

[0060]

[0061] [Formula 1-3]

[0062]

[0063] [Formula 1-4]

[0064]

[0065] in

[0066] R 1 To R 7 Each is independently a C1-C7 alkyl or a C2-C7 alkenyl.

[0067] In particular, in Formulas 1-1 to 1-4, R 1 To R 7 Each may independently be a C1-C5 alkyl group or a C2-C5 alkenyl group.

[0068] In particular, in Formulas 1-1 to 1-4, R 1 To R 7 Each may independently be a C1-C5 alkyl group.

[0069] In particular, in Formulas 1-1 to 1-4, R 1 and R 3 may each independently be a C2-C5 alkenyl group; R2 may be a C1-C5 alkyl group or a C2-C5 alkenyl group; and R 4 To R 7 Each may independently be a C1-C5 alkyl group.

[0070] In particular, in Formulas 1-1 to 1-4, R 1 To R 7 Each may independently be a C1-C3 alkyl group.

[0071] In particular, in Formulas 1-1 to 1-4, R 1 and R 3 may be independently C2-C3 alkenyl; R 2 may be a C1-C3 alkyl group or a C2-C3 alkenyl group; and R 4 To R 6 may each independently be a C1-C3 alkyl group; and R 7 It may be a C2-C3 alkyl group. In particular, in Formulas 1-1 to 1-4, R 1 To R 6 may each independently be a C1-C3 alkyl group; and R 7 It may be a C2-C3 alkyl group.

[0072] In particular, the silylcyclodisilazane compound of Formula 1 according to the present invention may be selected from the following compounds, but is not limited thereto:

[0073]

[0074] The silylcyclodisilazane compound of Formula 1 according to the exemplary embodiment of the present invention may be prepared through a conventional organic chemical reaction known to those skilled in the art.

[0075] In addition, the present invention provides a composition for depositing a silicon-containing thin film comprising a silylcyclodisilazane compound, which has excellent reactivity and thermal stability and exists mainly as a liquid at room temperature and is therefore easy to handle, as a precursor for depositing a thin film, the compound is represented by the following Formula 2:

[0076] [Formula 2]

[0077]

[0078] in

[0079] R 11 To R 17 Each is independently hydrogen, C1-C7 alkyl, C3-C7 cycloalkyl or C2-C7 alkenyl;

[0080] R 18is hydrogen, C1-C7 alkyl, C3-C7 cycloalkyl, C2-C7 alkenyl or -SiR a R b R c ;as well as

[0081] R a , R b and R c Each is independently hydrogen, C1-C7 alkyl, C3-C7 cycloalkyl or C2-C7 alkenyl;

[0082] The premise is that when R 11 To R 14 When all R 18 Not-SiR a R b R c .

[0083] The silylcyclodisilazane compound contained in the composition for depositing the silicon-containing film according to the present invention has a Si3N2 molecular skeleton, and the reactivity can be controlled by adjusting the symmetry and asymmetry of the compound according to the substituent group, and has a low activation energy due to the structure in which the silyl substituent is introduced into the nitrogen atom of the cyclodisilazane, and thus a high-quality silicon-containing film can be easily deposited at a high deposition rate. In addition, the silylcyclodisilazane compound of formula 2 according to the present invention is a compound that is mainly in liquid form at room temperature and normal pressure, has excellent volatility, and has a high content of silicon atoms in the molecule. Therefore, the composition for depositing a silicon-containing film containing the silylcyclodisilazane compound of formula 2 is not only easy to deposit a high-quality silicon-containing film at a high deposition rate, but also can manufacture a film with high durability and excellent purity due to excellent thermal stability.

[0084] In order to produce an excellent silicon-containing thin film, preferably in the above formula 2 according to the present invention, R 11 To R 13 and R 15 To R 17 may be independently hydrogen, C1-C7 alkyl, C3-C7 cycloalkyl or C2-C7 alkenyl; R 14 may be hydrogen; and R 18 It may be a C1-C7 alkyl group, a C3-C7 cycloalkyl group or a C2-C7 alkenyl group.

[0085] In order to produce an excellent silicon-containing thin film, preferably in Formula 2 according to the present invention, R 11 To R 14 may be independently C1-C7 alkyl, C3-C7 cycloalkyl or C2-C7 alkenyl; R 15 To R 17may each independently be hydrogen, C1-C7 alkyl, C3-C7 cycloalkyl or C2-C7 alkenyl; and R 18 It may be a C1-C7 alkyl group, a C3-C7 cycloalkyl group or a C2-C7 alkenyl group.

[0086] In order to produce an excellent silicon-containing thin film, preferably in Formula 2 according to the present invention, R 11 and R 13 may be independently C1-C7 alkyl or C2-C7 alkenyl; R 12 and R 14 R 15 It can be a C1-C7 alkyl group or a C2-C7 alkenyl group; R 16 and R 17 may each independently be hydrogen, C1-C7 alkyl or C2-C7 alkenyl; and R 18 It can be a C1-C7 alkyl group or a C2-C7 alkenyl group. More preferably, R 11 and R 13 can each independently be a C1-C5 alkyl group; R 12 and R 14 can be independently hydrogen or C1-C5 alkyl; R 15 It can be a C1-C5 alkyl group; R 16 and R 17 may each independently be hydrogen or C1-C5 alkyl; and R 18 It may be a C1-C5 alkyl group.

[0087] In order to produce an excellent silicon-containing thin film, preferably in Formula 2 according to the present invention, R 11 To R 13 and R 15 To R 17 may be independently hydrogen, C1-C7 alkyl, C3-C7 cycloalkyl or C2-C7 alkenyl; R 14 It can be hydrogen; R 18 Can be -SiR a R b R c ; R a may be a C1-C7 alkyl group or a C2-C7 alkenyl group; and R b and R c They may each independently be hydrogen, C1-C7 alkyl or C2-C7 alkenyl.

[0088] More preferably, R 11 and R 13 may be independently C1-C7 alkyl or C2-C7 alkenyl; R 12 R may be hydrogen, C1-C7 alkyl or C2-C7 alkenyl;14 It can be hydrogen; R 15 It can be a C1-C7 alkyl group or a C2-C7 alkenyl group; R 16 and R 17 R 18 Can be -SiR a R b R c ; R a may be a C1-C7 alkyl group or a C2-C7 alkenyl group; and R b and R c They may each independently be hydrogen, C1-C7 alkyl or C2-C7 alkenyl.

[0089] Still more preferably, R 11 and R 13 can each independently be a C1-C5 alkyl group; R 12 It can be hydrogen or C1-C5 alkyl; R 14 It can be hydrogen; R 15 It can be a C1-C5 alkyl group; R 16 and R 17 can be independently hydrogen or C1-C5 alkyl; R 18 Can be -SiR a R b R c ; R a may be a C1-C5 alkyl group; and R b and R c They may each independently be hydrogen or a C1-C5 alkyl group.

[0090] In terms of a precursor for depositing a thin film having more excellent characteristics, still more preferably, the silylcyclodisilazane compound of Formula 2 according to the present invention can be represented by the following Formula 2-1:

[0091] [Formula 2-1]

[0092]

[0093] Among them, R 11 and R 13 Each is independently a C1-C3 alkyl group; R 12 is hydrogen or C1-C3 alkyl; R 15 is a C1-C3 alkyl group; R 16 and R 17 Each is independently hydrogen or C1-C3 alkyl; R 18 is C1-C3 alkyl or -SiR a R b R c ; R ais a C1-C3 alkyl group; and R b and R c Each is independently hydrogen or C1-C3 alkyl.

[0094] In an exemplary embodiment of the present invention, R 18 It may be a C2-C3 alkyl group.

[0095] In an exemplary embodiment of the present invention, R 18 Can be -SiR a R b R c ; R a may be a C1-C3 alkyl group; and R b and R c They may each independently be hydrogen or a C1-C3 alkyl group.

[0096] In terms of a precursor for depositing a thin film having more excellent characteristics, still more preferably, the silylcyclodisilazane compound of Formula 2 according to the present invention can be represented by the following Formula 2-2:

[0097] [Formula 2-2]

[0098]

[0099] Among them, R 15 is a C1-C3 alkyl group; R 16 and R 17 are each independently hydrogen or C1-C3 alkyl; and R 18 It is a C1-C3 alkyl group.

[0100] In an exemplary embodiment of the present invention, R 18 It may be a C2-C3 alkyl group.

[0101] In particular, the silylcyclodisilazane compound according to the present invention can be selected from the following compounds, but is not limited thereto:

[0102]

[0103] The composition for depositing a silicon-containing thin film according to the present invention necessarily includes the silylcyclodisilazane compound of Formula 2 above as a precursor, and may include one or more silylcyclodisilazane compounds, and the content of the silylcyclodisilazane compound in the composition for depositing a silicon-containing thin film may be included in the range recognized by those skilled in the art, taking into account the film formation conditions of the thin film or the thickness and characteristics of the thin film.

[0104] In addition, the present invention provides a method for manufacturing a silicon-containing thin film using the composition for depositing a silicon-containing thin film according to the present invention.

[0105] The method for manufacturing a silicon-containing thin film according to an exemplary embodiment can manufacture a thin film using a composition for depositing a silicon-containing thin film according to the present invention, the silylcyclodisilazane compound of Formula 2 above, which is liquid at room temperature and has high volatility and excellent thermal stability, is included as a precursor, and therefore, a high-purity silicon-containing thin film that is easy to handle the precursor can be manufactured, a silicon-containing thin film can be manufactured under various conditions, has a high silicon content and a deposition rate, and has excellent step coverage.

[0106] The silicon-containing film according to the exemplary embodiment may be any film that can be manufactured within the scope recognized by those skilled in the art. In particular, the silicon-containing film may be a silicon oxide (SiO2) film, a silicon oxycarbide (SiOC) film, a silicon nitride (SiN) film, a silicon oxynitride (SiON) film, a silicon nitride carbon (SiCN) film, or a silicon carbide (SiC) film, etc., and in addition, various high-quality silicon-containing films may be manufactured within the scope recognized by those skilled in the art.

[0107] The method for manufacturing the silicon-containing thin film according to the exemplary embodiment may be any method within the scope recognized by those skilled in the art, and the method may be preferably performed by atomic layer deposition (ALD), chemical vapor deposition (CVD), metal organic chemical vapor deposition (MOCVD), low pressure chemical vapor deposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD) or plasma enhanced atomic layer deposition (PEALD). In order to make the thin film easy to deposit and to make the manufactured thin film have excellent characteristics, plasma enhanced atomic layer deposition (PEALD) or plasma enhanced chemical vapor deposition (PECVD) is preferred.

[0108] The method for manufacturing a silicon-containing thin film according to an exemplary embodiment may specifically include: a) heating and maintaining the temperature of a substrate installed in a chamber at 30 to 400° C.; b) contacting the substrate with a composition for depositing a silicon-containing thin film according to an exemplary embodiment of the present invention to be adsorbed on the substrate; and c) injecting a reaction gas to deposit the silicon-containing thin film on the substrate.

[0109] Preferably, when the silicon-containing film according to the exemplary embodiment of the present invention is manufactured by plasma enhanced atomic layer deposition (PEALD) or plasma enhanced vapor deposition (PECVD), the method may further include generating plasma after step a). In addition, in step b), the composition for depositing the silicon-containing film may be injected together with a carrier gas.

[0110] In the method for manufacturing a silicon-containing film according to an exemplary embodiment, the deposition conditions may be adjusted according to the desired structure or thermal characteristics of the film. As deposition conditions according to an exemplary embodiment, the input flow rate of the composition containing a silylcyclodisilazane for depositing a silicon-containing film, the input flow rate of the reaction gas, the input flow rate of the carrier gas, the pressure, the RF power, the substrate temperature, etc. may be exemplified, and as a non-limiting example of the deposition conditions, the following may be adjusted within a range (but not limited thereto): the input flow rate of the composition for depositing a silicon-containing film is 10 to 1000 cc / min, the carrier gas is 10 to 1000 cc / min, the reaction gas flow rate is 1 to 1000 cc / min, the pressure is 0.5 to 10 Torr, the RF power is 200 to 1000 W, and the substrate temperature is 30 to 400° C., preferably 100 to 350° C.

[0111] Considering the material of the silicon-containing thin film to be manufactured, the reaction gas used in the method for manufacturing the silicon-containing thin film according to the exemplary embodiment can be used as long as it is a gas generally used together with the silicon precursor. Specific examples of the reaction gas may include, but are not limited to, any one or two or more selected from the following: oxygen (O2), ozone (O3), distilled water (H2O), hydrogen peroxide (H2O2), nitric oxide (NO), nitrous oxide (N2O), nitrogen dioxide (NO2), ammonia (NH3), nitrogen (N2), hydrazine (N2H4), amines, diamines, carbon monoxide (CO), carbon dioxide (CO2), C1-C 12 Saturated or unsaturated hydrocarbons, hydrogen, argon and helium. Examples of the carrier gas may include, but are not limited to, one or two or more selected from argon, helium and nitrogen.

[0112] The substrate used in the method for manufacturing a silicon-containing thin film according to an exemplary embodiment may be a substrate including: 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 such as polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyether sulfone (PES) and polyester, but is not limited thereto.

[0113] Furthermore, in addition to directly forming the silicon-containing film on the substrate, a plurality of conductive layers, dielectric layers, insulating layers, etc. may be formed between the substrate and the silicon-containing film.

[0114] Hereinafter, the present invention will be described in detail by the following examples. Prior to this, based on the principle that the inventor can appropriately define the concept of the term to describe his own invention in the best way, the terms and words used in this specification and claims should not be interpreted as general or dictionary meanings, but should be interpreted as meanings and concepts that conform to the technical ideas of the present invention.

[0115] Therefore, the configurations illustrated in the examples described herein and the drawings are merely the most preferred exemplary embodiments of the present invention, but do not represent all the technical spirits of the present invention. Therefore, it should be understood that when submitting this application, there are various equivalents and modified examples to replace these.

[0116] In addition, the following examples are all implemented by the known plasma enhanced atomic layer deposition (PEALD) using a commercially available 200 mm single wafer type ALD equipment (CN1, Atomic Premium) in a showerhead mode. In addition, it can be implemented by the known plasma enhanced chemical vapor deposition (PECVD) using a commercially available 200 mm single wafer type CVD equipment (CN1, Atomic Premium) in a showerhead mode.

[0117] The thickness of the deposited silicon-containing films was measured using an ellipsometer (OPTI-PROBE 2600, THERMA-WAVE), and the film characteristics were analyzed using infrared spectroscopy (IFS66V / S & Hyperion 3000, Bruker Optics) and X-ray photoelectron spectroscopy.

[0118] [Example 1] Synthesis of 1-isopropyl-3-dimethylsilyl-2,2,4-trimethylcyclodisilazane

[0119] Under anhydrous and inert atmosphere, 150g (1.59mol) of dimethylchlorosilane (SiH(CH3)2Cl) and 800g (11.1mol) of n-pentane are added to a flame-dried 2000mL flask, and 187.4g (3.17mol) of isopropylamine ((CH3)2CHNH2) is slowly added thereto while being maintained at -25°C, followed by stirring for 3 hours. After stirring is complete, the isopropylamine hydrochloride salt ((CH3)2CHNH3Cl) is removed by filtration, and n-pentane is removed from the obtained filtrate under reduced pressure. Tetrahydrofuran (THF) is added to the recovered dimethylsilyl isopropylamine (SiH(CH3)2NHCH(CH3)2), and 394g (1.34mol) of 21.78% n-butyllithium is slowly added thereto while being maintained at -25°C with stirring. After addition is complete, the reaction solution is slowly raised to room temperature and stirred at room temperature for 6 hours. After stirring, 172.80 g (1.34 mol) of dichlorodimethylsilane (Si(CH3)2Cl2) is slowly added while maintaining at -25°C. After the addition is complete, the reaction solution is slowly raised to room temperature and stirred at room temperature for 6 hours. After the stirring is complete, the resulting lithium chloride salt (LiCl) is removed by filtration, and tetrahydrofuran (THF) is removed from the obtained filtrate under reduced pressure. The recovered dimethylsilyldimethylchlorosilylisopropylamine (SiH(CH3)2NCH(CH3)2Si(CH3)2Cl) is mixed with n-pentane, and then 41.08 g (2.41 mol) of ammonia (NH3) is slowly added while stirring at -25°C. After the addition is complete, the reaction solution is slowly raised to room temperature and stirred at room temperature for 6 hours. After the stirring is complete, the resulting ammonium chloride salt (NH4Cl) is removed by filtration, and n-pentane is removed from the obtained filtrate under reduced pressure. The recovered (dimethylsilyl)(aminodimethylsilyl)isopropylamine (SiH(CH3)2NCH(CH3)2Si(CH3)2NH2) was mixed with tetrahydrofuran, and 349.06 g (1.19 mol) of 21.78% n-butyl lithium was slowly added thereto under stirring at -25°C. After stirring for 3 hours, 135.95 g (1.18 mol) of dichloromethylsilane (SiH(CH3)Cl2) was slowly added under stirring at -25°C. After the addition was completed, the reaction solution was slowly raised to room temperature and stirred at room temperature for 6 hours. After the stirring was completed, the obtained lithium chloride salt (LiCl) was removed by filtration, tetrahydrofuran (THF) was removed from the obtained filtrate under reduced pressure, and then distilled under reduced pressure to obtain 75 g (0.32 mol) of 1-isopropyl-3-dimethylsilyl-2,2,4-trimethylcyclodisilazane (Si(CH3)2NCH(CH3)2SiHCH3NSiH(CH3)2) (yield 54%).

[0120] 1 H-NMR(C6D6):δ0.16(d,6H(NSiH(C H 3)2),0.28(d,6H(N,N-Si(C H 3)2),0.32(s,3H(N,N-SiHC H 3)),1.00(d,6H(NCH(C H 3)2),3.21(m,1H(-NC H )),4.75(m,1H(NSi H (CH3)2),5.50(s,1H(N,N-Si H CH3).

[0121] [Example 2] Synthesis of 1-isopropyl-3-trimethylsilyl-2,4-dimethylcyclodisilazane

[0122] Under anhydrous and inert atmosphere, 535 g (1.61 mol) of bis (dimethylaminomethylsilyl) trimethylsilylamine (((CH3)2N(CH3)HSi)2NSi(CH3)3) and 732 g (10.15 mol) of n-pentane were added to a flame-dried 2000 mL flask, and 292.3 g (8.12 mol) of hydrogen chloride (HCl) was slowly added thereto while maintaining at -40°C, followed by stirring for 3 hours. Dimethylamine hydrochloride salt ((CH3)2NH2Cl) was removed by filtration, and n-pentane was removed from the obtained filtrate under reduced pressure. The recovered bis(chloromethylsilyl)trimethylsilylamine ((ClCH3)HSi)2NSi(CH3)3) was mixed with n-pentane, and then 240.91 g (4.03 mol) of isopropylamine ((CH3)2CHNH2) was slowly added while maintaining at -25°C with stirring. After the addition was completed, the reaction solution was slowly raised to room temperature and stirred at room temperature for 3 hours. After stirring, the hydrochloric acid isopropylamine salt ((CH3)2CHNH3Cl) was removed by filtration.

[0123] The recovered (chloromethylsilyl)(isopropylaminomethylsilyl)trimethylsilylamine ((ClCH3)HSi)((CH3)2CHNH(CH3)HSi)NSi(CH3)3) solution was slowly added to 518.9 g (1.35 mol) of 1.70 M tert-butyl lithium while maintaining at -25°C. After the addition was completed, the reaction solution was slowly raised to room temperature and then stirred at room temperature for 6 hours. After the stirring was completed, the resulting lithium chloride salt (LiCl) was removed by filtration, the solvent was removed from the obtained filtrate under reduced pressure, and then distilled under reduced pressure to obtain 103 g (0.44 mol) of 1-isopropyl-3-trimethylsilyl-2,4-dimethylcyclodisilazane (Si(CH3)3N(SiH(CH3))2NCH(CH3)2) (yield 32%).

[0124] 1 H-NMR(C6D6):δ0.10(s,9H(NSi-(C H 3)3),0.33(d,6H(N,N-SiH(C H 3)),1.00(d,6H,(NCH(C H 3)2),3.15(m,1H(-NC H )),5.49(s,1H(N,N-Si H (CH3)),5.52(s,1H(N,N-Si H (CH3)).

[0125] [Example 3] Synthesis of 1-isopropyl-3-methylsilyl-2,4-dimethylcyclodisilazane

[0126] Under anhydrous and inert atmosphere, 350g (1.26mol) of tris (dimethylaminomethylsilyl) amine (((CH3)2NSiHCH3)3N) and 725.07g (10.05mol) of n-pentane are added to a flame-dried 2000mL flask, and 263.8g (7.54mol) of hydrogen chloride (HCl) is slowly added thereto while being maintained at -40°C, followed by stirring for 3 hours. Dimethylamine hydrochloride salt ((CH3)2CHNH3Cl) is removed by filtration, and n-pentane is removed from the filtrate obtained under reduced pressure. The recovered tris (chloromethylsilyl) amine ((ClCH3SiH)3N) is mixed with n-pentane, and 148.51g (2.51mol) of isopropylamine ((CH3)2CHNH2) is slowly added while being maintained at -25°C with stirring. After the addition is complete, the reaction solution is slowly raised to room temperature and stirred at room temperature for 3 hours. After stirring is completed, the isopropylamine hydrochloride salt ((CH3)2CHNH3Cl) is removed by filtration. The recovered [bis(chloromethylsilyl)](isopropylaminomethylsilyl)amine ((ClCH3SiH)2((CH3)2CHNHCH3SiH)N) solution is slowly added to 481.79g (1.26mol) of 1.70M tert-butyl lithium while being maintained at -25°C. After the addition is completed, the reaction solution is slowly raised to room temperature, and then stirred at room temperature for 6 hours. After stirring is completed, the resulting lithium chloride salt (LiCl) is removed by filtration. The solvent is removed from the obtained filtrate under reduced pressure, mixed with tetrahydrofuran (THF), and then 14.98g (1.88mol) of lithium hydride (LiH) is added under stirring at room temperature, followed by stirring for 3 hours. The resulting lithium chloride salt (LiCl) is removed by filtration. The obtained filtrate was distilled under reduced pressure to obtain 103 g (0.5 mol) of 1-isopropyl-3-methylsilyl-2,4-dimethylcyclodisilazane (SiH2CH3N(SiHCH3)2NCH(CH3)2) (yield 40%).

[0127] 1 H-NMR(C6D6):δ0.15(t,3H(NSiH2(C H 3)),0.28(s,6H(N,N-SiH(C H 3)),0.98(d,6H,(NCH(C H 3)2),3.2(m,1H(NC H (CH3)),5.47(m,2H(Si H (CH3)),4.6(m,2H NSi H 2(CH3)).

[0128] [Example 4] Synthesis of 1-ethyl-3-trimethylsilyl-2,4-dimethylcyclodisilazane

[0129] Under anhydrous and inert atmosphere, 535g (2.03mol) of bis(dimethylaminomethylsilyl)trimethylsilylamine (((CH3)2N(CH3HSi)2NSi(CH3)3) and 732g (10.15mol) of n-pentane are added to a flame-dried 2000mL flask, and 292.3g (8.12mol) of hydrogen chloride (HCl) is slowly added while maintaining at -40°C, followed by stirring for 3 hours. Dimethylamine hydrochloride salt ((CH3)2NH2Cl) is removed by filtration, and n-pentane is removed from the obtained filtrate under reduced pressure. The recovered bis(chloromethylsilyl)trimethylsilylamine ((ClCH3)HSi)2NSi(CH3)3) is mixed with n-pentane, and then 136.6g (3.03mol) of ethylamine (CH3CH2NH2) is slowly added while maintaining at -25°C with stirring. After the addition was completed, the reaction solution was slowly raised to room temperature and stirred at room temperature for 3 hours. After stirring, ethylamine hydrochloride salt (CH3CH2NH3Cl) was removed by filtration. The recovered (chloromethylsilyl)(ethylaminomethylsilyl)trimethylsilylamine ((Cl(CH3)HSi)((CH3CH2NH(CH3)HSi)NSi(CH3)3) solution was slowly added to 547.49 g (1.43 mol) of 1.70 M tert-butyl lithium while maintaining at -25°C. After the addition was completed, the reaction solution was slowly raised to room temperature and then stirred at room temperature for 6 hours. After the stirring was completed, the resulting lithium chloride salt (LiCl) was removed by filtration, the solvent was removed from the obtained filtrate under reduced pressure, and then distilled under reduced pressure to obtain 258 g (1.18 mol) of 1-ethyl-3-trimethylsilyl-2,4-dimethylcyclodisilazane (Si(CH3)3N(SiH(CH3))2)N(CH2CH3) (yield 83%).

[0130] 1 H-NMR(C6D6):δ0.10(s,9H(NSi-(C H 3)3),0.28(d,6H(N,N-SiH(C H 3)),0.99(t,2H(NC H 2CH3),2.74(q,3H(NCH2C H 3)),5.48(d,1H(N,N-Si H (CH3)),5.50(s,1H(N,N-Si H (CH3)).

[0131] [Example 5] Deposition of silicon oxide film by plasma enhanced atomic layer deposition (PEALD) using silylcyclodisilazane compounds

[0132] In a conventional plasma enhanced atomic layer deposition (PEALD) apparatus using known plasma enhanced atomic layer deposition (PEALD), film formation evaluation was performed using the silylcyclodisilazane compound according to the present invention as a composition for forming a silicon oxide film. Oxygen was used as a reaction gas along with plasma, and argon, which is an inert gas, was used for purging purposes.

[0133] The specific method used to deposit the silicon oxide film is shown in Table 1 below.

[0134] [Table 1]

[0135] Deposition conditions of silicon oxide films

[0136]

[0137] The thickness of the deposited films was measured using an ellipsometer, and the formation of SiO2 films was analyzed using an infrared spectrophotometer. Figure 3 The graph shows the deposition rate of the silicon oxide film analyzed by ellipsometer, and the thickness of the film is shown. When the silicon oxide film is deposited using the silylcyclodisilazane compound according to the present invention as a precursor, the thickness of the film is 215 to 250 nm. Between 2.15 and 2.25 based on deposition cycles Therefore, it is confirmed that the silylcyclodisilazane compound according to the present invention can be effectively used as a precursor for depositing a silicon oxide film in all application fields requiring a silicon oxide thin film with a high deposition rate. Figure 4 The results of analyzing the formation of the deposited silicon oxide film using an infrared spectrometer are shown, and it is illustrated that all the deposited films formed silicon oxide films, and no impurity peaks such as CH and Si-OH were observed [(top) 1-isopropyl-3-trimethylsilyl-2,4-dimethylcyclodisilazane; (middle) 1-isopropyl-3-trimethylsilyl-2,2,4,4-tetramethylcyclodisilazane; (bottom) 1,3-bis(trimethylsilyl)-2,4-dimethylcyclodisilazane]. The composition of the deposited silicon oxide film was also analyzed using X-ray photoelectron spectroscopy, and the results are shown in Table 2 below. As shown in Table 2 below, it can be confirmed that the ratio of oxygen to silicon in the film deposited using the silylcyclodisilazane compound according to the present invention as a precursor is 2 (67:33), and the content of carbon and nitrogen is 0%, thereby forming a high-purity silicon oxide film.

[0138] [Table 2]

[0139] Composition of silicon oxide films using X-ray photoelectron spectroscopy

[0140]

[0141] That is, the silylcyclodisilazane compound according to the present invention forms a high-purity silicon oxide thin film at a high deposition rate through a plasma atomic layer deposition process, which has been confirmed to have high utilization value.

[0142] [Example 6] Deposition of silicon nitride film by plasma enhanced atomic layer deposition (PEALD) using silylcyclodisilazane compound

[0143] In a conventional plasma enhanced atomic layer deposition (PEALD) apparatus using known plasma enhanced atomic layer deposition (PEALD), film formation evaluation was performed using a 1-isopropyl-3-trimethylsilyl-2,4-dimethylcyclodisilazane compound as a composition for forming a silicon nitride film. Nitrogen gas was used as a reaction gas and a purge gas.

[0144] The silicon substrate is maintained at a temperature of 350°C, and the 1-isopropyl-3-trimethylsilyl-2,4-dimethylcyclodisilazane compound is loaded into a stainless steel bubbling container and maintained at a temperature of 58°C. First, the silicon precursor compound evaporated in the stainless steel bubbling container is transferred to the silicon substrate using nitrogen (50sccm) as a carrier gas to be adsorbed on the silicon substrate. Secondly, the unadsorbed silicon precursor compound is removed using nitrogen (6000sccm) for about 32 seconds. Again, a silicon nitride film is formed by applying 75W plasma for 60 seconds under nitrogen (6000sccm) conditions. Finally, nitrogen (6000sccm) is used to remove reaction byproducts and residual reaction gases for about 20 seconds. The above process is a cycle, and this cycle is repeated several times to form a silicon nitride film.

[0145] The specific method used to deposit the silicon nitride film is shown in Table 3 below.

[0146] [Table 3]

[0147] Deposition conditions of silicon nitride films

[0148]

[0149] The thickness and refractive index of the deposited silicon nitride film were measured using an ellipsometer, and the formation of the silicon nitride film and the composition of the film were analyzed using an infrared spectrophotometer and an X-ray photoelectron spectroscopy. Under the analysis of the ellipsometer, the film thickness on the flat wafer during 240 cycles was And the growth rate of each cycle is In addition, the refractive index is 2.0, showing the characteristics of a silicon nitride thin film.

[0150] In addition, if Figure 5 As shown in the figure, under the analysis of the infrared spectrophotometer, Si-N bonds were confirmed, and only a small amount of Si-H peaks were observed. The composition of the film analyzed by X-ray photoelectron spectroscopy is shown in Table 4. As a result, it can be confirmed that a silicon nitride film is formed in the film with a silicon / nitrogen ratio of 0.72, which is close to an ideal silicon nitride film.

[0151] [Table 4]

[0152] Composition of silicon nitride thin films using X-ray photoelectron spectroscopy

[0153]

[0154] That is, it has been confirmed that the silylcyclodisilazane compound according to the present invention has high utilization value in forming a high-purity silicon nitride film by a plasma atomic layer deposition process. The foregoing description of the present invention is only for illustrative purposes, and a person skilled in the art to which the present invention belongs will understand that other specific forms can be easily modified without changing the technical spirit or basic features of the present invention. Therefore, it should be understood that the embodiments described above are illustrative in all aspects and not restrictive.

Claims

1. A silylcyclodisilazane compound represented by the following formula 1: [Formula 1] in R 1 To R 6 are each independently hydrogen, C1-C7 alkyl or C2-C7 alkenyl; and R 7 It is a C1-C7 alkyl group or a C2-C7 alkenyl group.

2. The silylcyclodisilazane compound according to claim 1, wherein R 1 and R 3 Each is independently a C1-C5 alkyl or a C2-C5 alkenyl; R 2 is hydrogen, C1-C5 alkyl or C2-C5 alkenyl; R 4 is C1-C5 alkyl or C2-C5 alkenyl; R 5 and R 6 are each independently hydrogen, C1-C5 alkyl or C2-C5 alkenyl; and R 7 It is a C1-C5 alkyl group or a C2-C5 alkenyl group.

3. The silylcyclodisilazane compound according to claim 1, wherein The silylcyclodisilazane compound is selected from the following compounds:

4. A composition for depositing a silicon-containing thin film, comprising a silylcyclodisilazane compound represented by the following formula 2: [Formula 2] in R 11 To R 17 Each is independently hydrogen, C1-C7 alkyl or C2-C7 alkenyl; R 18 is hydrogen, C1-C7 alkyl, C2-C7 alkenyl or -SiR a R b R c ;as well as R a , R b and R c Each is independently hydrogen, C1-C7 alkyl or C2-C7 alkenyl; The premise is that when R 11 To R 14 When all are C1-C7 alkyl, R 18 Not-SiR a R b R c .

5. The composition for depositing a silicon-containing thin film according to claim 4, wherein R 11 and R 13 Each is independently a C1-C7 alkyl or a C2-C7 alkenyl; R 12 and R 14 Each is independently hydrogen, C1-C7 alkyl or C2-C7 alkenyl; R 15 is C1-C7 alkyl or C2-C7 alkenyl; R 16 and R 17 are each independently hydrogen, C1-C7 alkyl or C2-C7 alkenyl; and R 18 It is a C1-C7 alkyl group or a C2-C7 alkenyl group.

6. The composition for depositing a silicon-containing thin film according to claim 4, wherein R 11 and R 13 Each is independently a C1-C7 alkyl or a C2-C7 alkenyl; R 12 is hydrogen, C1-C7 alkyl or C2-C7 alkenyl; R 14 is hydrogen; R 15 is C1-C7 alkyl or C2-C7 alkenyl; R 16 and R 17 Each is independently hydrogen, C1-C7 alkyl or C2-C7 alkenyl; R 18 -SiR a R b R c ; R a is C1-C7 alkyl or C2-C7 alkenyl; and R b and R c Each is independently hydrogen, C1-C7 alkyl or C2-C7 alkenyl.

7. The composition for depositing a silicon-containing thin film according to claim 4, wherein The silylcyclodisilazane compound is selected from the following compounds: 8 . A method for manufacturing a silicon-containing thin film, using the composition for depositing a silicon-containing thin film according to claim 4 .

9. The method for producing a silicon-containing thin film according to claim 8, wherein: The method is performed by atomic layer deposition (ALD), chemical vapor deposition (CVD), metal organic chemical vapor deposition (MOCVD), low pressure chemical vapor deposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD) or plasma enhanced atomic layer deposition (PEALD).

10. The method for producing a silicon-containing thin film according to claim 8, wherein: The silicon-containing film is a silicon oxide (SiO2) film, a silicon oxycarbide (SiOC) film, a silicon nitride (SiN) film, a silicon oxynitride (SiON) film, a silicon carbonitride (SiCN) film or a silicon carbide (SiC) film.

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