Cyclic disilazane compound, composition for depositing silicon-containing thin film comprising same, and method for manufacturing silicon-containing thin film using same

Abstract

The present invention relates to a cyclic disilazane compound, a composition for depositing a silicon-containing thin film comprising the same, and a method for manufacturing a silicon-containing thin film using the same, in which the cyclic disilazane compound according to the present invention is a thermally stable, highly reactive and volatile compound and is in a liquid state at room temperature and at a pressure allowing easy handling, and a high-purity silicon-containing thin film having excellent physical characteristics and electrical characteristics can be formed by various deposition methods.

Description

Technical Field

[0001] The following disclosure relates to novel cyclodisilazane compounds, compositions for depositing silicon-containing films containing the same, and methods for producing silicon-containing films using the same. Background Art

[0002] Silicon-containing thin films are manufactured into various forms such as silicon films, silicon oxide films, silicon nitride films, silicon carbonitride films, and silicon oxynitride films by various deposition methods in the semiconductor field, and are used as semiconductor substrates, diffusion masks, anti-oxidation films, dielectric films, etc. in semiconductor technologies such as flat panel displays including microelectronic devices such as RAM (memory and logic chips) and thin film transistors (TFTs), and in the solar energy field. Recently, polycrystalline silicon thin films have been used for thin film transistors (TFTs), solar cells, etc., and their applications are becoming increasingly diverse.

[0003] In order to deposit high-quality silicon-containing thin films, various silicon precursors, such as aminosilanes, such as butylaminosilane (BAS), bis-tert-butylaminosilane (BTBAS), dimethylaminosilane (DMAS), bisdimethylaminosilane (BDMAS), trisdimethylaminosilane (3-DMAS), diethylaminosilane (DEAS), bisdiethylaminosilane (BDEAS), dipropylaminosilane (DPAS), and diisopropylaminosilane (DIPAS), are being studied and developed in addition to conventional silicon precursors such as silane, disilane, and halosilanes.

[0004] Representative technologies known for producing silicon-containing thin films include: metalorganic chemical vapor deposition (MOCVD) in which a silicon precursor and a reactive gas in the form of a mixed gas react to form a film on a substrate surface, or react directly on the surface to form a film; and atomic layer deposition (ALD) in which a silicon precursor in the form of a gas is physically or chemically adsorbed on a substrate surface and then a film is formed by subsequently adding a reactive gas, as well as various thin film manufacturing technologies using techniques such as low pressure chemical vapor deposition (LPCVD); and plasma-enhanced chemical vapor deposition (PECVD) and plasma-enhanced atomic layer deposition (PEALD) that allow deposition at low temperatures using plasma are applied to next-generation semiconductor and display device manufacturing processes and are used for depositing thin films having uniform and excellent characteristics in terms of ultrafine pattern formation and nanometer thickness.

[0005] To form high-quality silicon-containing thin films, the precursor ① has excellent volatility, wherein the compound is in liquid form at room temperature and pressure, ② has high thermal stability and low activation energy of the compound itself to have excellent reactivity, ③ does not produce non-volatile byproducts during the film deposition process, and ④ should be easy to handle, transport, and store.

[0006] However, due to the miniaturization and increased aspect ratio of components caused by the ultra-high integration of components and the diversification of component materials, technology is needed to form ultra-fine films with uniform small thickness and excellent electrical properties at a desired low temperature. Therefore, high-temperature processes at 600°C or higher using conventional silicon precursors, step coverage, etching characteristics, and physical and electrical properties of the films become problems.

[0007] However, even when forming an ultrafine thin film having a uniform small thickness and excellent electrical characteristics at the low temperature required for devices, productivity due to the low film formation speed becomes a problem, and therefore, development of new silicon precursors with improved performance is required. Summary of the Invention

[0008] Technical issues

[0009] One embodiment of the present invention is directed to providing novel cyclodisilazane compounds.

[0010] Specifically, one embodiment of the present invention is directed to providing a cyclodisilazane compound that not only has excellent volatility but also has a high vapor pressure and is liquid at room temperature.

[0011] Specifically, one embodiment of the present invention is directed to providing a precursor compound that has good reactivity with a substrate and can form a stable silicon-containing thin film with high reactivity over a wide temperature range.

[0012] Another embodiment of the present invention is directed to providing a composition for depositing a silicon-containing thin film, comprising a cyclodisilazane compound having high thermal stability and reactivity.

[0013] Another embodiment of the present invention is directed to providing a method for manufacturing a silicon-containing thin film using a cyclodisilazane compound having high thermal stability and reactivity.

[0014] Yet another embodiment of the present invention is directed to providing a method for manufacturing a silicon-containing thin film using the above composition for depositing a silicon-containing thin film.

[0015] Technical Solution

[0016] In one general aspect, a cyclic disilazane compound represented by the following Chemical Formula 1 is provided:

[0017] [Chemical Formula 1]

[0018]

[0019] In Chemical Formula 1,

[0020] R 1 is a C1-C5 alkyl group or a C3-C7 cycloalkyl group;

[0021] R 2 is a C1-C5 alkyl group, a C3-C7 cycloalkyl group, or a C1-C5 alkoxy group;

[0022] R 3 and R 4 are independently hydrogen, C1-C5 alkyl, C3-C7 cycloalkyl, or C1-C5 alkoxy; and

[0023] R 5 and R 6 are independently C2-C5 alkyl, C3-C7 cycloalkyl, or C2-C5 alkenyl.

[0024] According to an exemplary embodiment, in Chemical Formula 1, R 1 Can be C1-C3 alkyl; R 2 to R 4 may be independently C1-C3 alkyl or C1-C3 alkoxy; and R 5and R 6 They may independently be C2-C3 alkyl or C2-C3 alkenyl.

[0025] According to an exemplary embodiment, the compound may be a compound represented by the following Chemical Formula 2-1 or 2-2:

[0026] [Chemical Formula 2-1]

[0027]

[0028] [Chemical Formula 2-2]

[0029]

[0030] In Chemical Formulas 2-1 and 2-2,

[0031] R 2 to R 4 are independently C1-C3 alkyl or C1-C3 alkoxy; and

[0032] R 7 It is a C2-C3 alkyl group or a C2-C3 alkenyl group.

[0033] The compound according to an exemplary embodiment may be at least one selected from the following structures:

[0034]

[0035]

[0036] In another general aspect, a composition for depositing a silicon-containing thin film includes a cyclic disilazane compound represented by the following Chemical Formula 3:

[0037] [Chemical Formula 3]

[0038]

[0039] In Chemical Formula 3,

[0040] R 11 is a C1-C5 alkyl group or a C3-C7 cycloalkyl group;

[0041] R 12 to R 14 are independently hydrogen, C1-C5 alkyl, C3-C7 cycloalkyl, or C1-C5 alkoxy; and

[0042] R 15 and R 16 are independently C1-C5 alkyl, C3-C7 cycloalkyl, or C2-C5 alkenyl.

[0043] According to an exemplary embodiment, in Chemical Formula 3 of the cyclodisilazane compound of the composition for depositing a silicon-containing thin film, R 11 Can be C1-C3 alkyl; R 12 to R 14 may be independently C1-C3 alkyl or C1-C3 alkoxy; and R 15 and R 16 They may independently be C1-C3 alkyl or C2-C3 alkenyl.

[0044] In the composition for depositing a silicon-containing thin film according to an exemplary embodiment, the cyclic disilazane compound may be at least one selected from the following structures:

[0045]

[0046]

[0047] In another general aspect, a method of making a silicon-containing thin film using the above-described compound is provided.

[0048] In yet another general aspect, a method of making a silicon-containing thin film using the composition for depositing a silicon-containing thin film is provided.

[0049] In a method of manufacturing a silicon-containing thin film according to an exemplary embodiment, the manufacturing method may be performed by, but is not limited to, 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).

[0050] In a method for manufacturing a silicon-containing thin film according to an exemplary embodiment, the silicon-containing thin film may be a silicon oxide film (SiO2), a silicon oxycarbide film (SiOC), a silicon nitride film (SiN), a silicon oxynitride film (SiON), a silicon carbonitride film (SiCN), a silicon carbide film (SiC), or the like.

[0051] Beneficial effects

[0052] Because the cyclodisilazane compound according to the present invention has high volatility, excellent thermal stability, and low activation energy, and therefore high reactivity, it is very useful as a precursor for depositing silicon-containing thin films. Furthermore, because the cyclodisilazane compound according to the present invention exists as a liquid at room temperature and under a pressure that allows for processing, it is easy to handle. Therefore, silicon-containing thin films produced using the cyclodisilazane compound according to the present invention as a precursor for thin film deposition have high purity and excellent physical and electrical properties.

[0053] Furthermore, since the composition for depositing a silicon-containing thin film according to the present invention includes a cyclodisilazane compound having high thermal stability and reactivity, a thin film having excellent physical and electrical properties such as excellent cohesion and excellent step coverage and having excellent purity and durability can be manufactured at a high deposition rate.

[0054] That is, according to the present invention, by using a cyclodisilazane compound as a precursor for depositing a thin film, a high-quality silicon-containing thin film having a high silicon content and excellent thermal stability and durability can be manufactured. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1 3 are thermogravimetric analysis (TGA) graphs of the cyclodisilazane compounds prepared in Examples 1 to 3.

[0056] Figure 2 is a differential scanning calorimetry (DSC) chart of the cyclodisilazane compounds prepared in Examples 1 to 3.

[0057] Figure 3 The results of infrared spectrophotometric analysis of the silicon oxide thin films produced in Examples 4 and 5 are shown.

[0058] Figure 4 3 is an image in which the step coverage of the silicon oxide thin film produced in Example 4 was observed by a transmission electron microscope. DETAILED DESCRIPTION

[0059] Hereinafter, the present invention will be described in detail with reference to the accompanying tables or drawings.

[0060] When the accompanying drawings are shown, they are provided by way of example so that the concept of the present invention can be fully conveyed to those skilled in the art. Therefore, the present invention is not limited to the accompanying drawings provided, but can be embodied in many different forms, and in order to make the spirit of the present invention clear, the accompanying drawings may be enlarged.

[0061] Unless otherwise defined, technical and scientific terms used herein have general meanings understood by those skilled in the art to which the present invention belongs, and descriptions of known functions and configurations that may unnecessarily obscure the subject matter of the present invention will be omitted in the following description and drawings.

[0062] Furthermore, unless the context indicates otherwise, singular forms used in this specification may be intended to include plural forms as well.

[0063] In addition, units not specifically mentioned in this specification are based on weight, and as an example, unless otherwise defined, units of % or ratio refer to weight % or weight ratio, and weight % refers to the weight % of any one component in the total composition.

[0064] The numerical ranges used in this specification include all values ​​within the range including the lower and upper limits, increments logically derived from the form and span of the defined range, all double-bound values, and all possible combinations of upper and lower limits within the numerical range defined in different forms.

[0065] In addition, the term "comprising" in this specification is an open description having equivalent meanings to terms such as "providing", "including", "having" or "characterized by", and does not exclude elements, materials or processes that are not further listed.

[0066] Furthermore, the term “substantially” in this specification means that other elements, materials or processes not listed with a particular element, material or process may be present in an amount that does not unacceptably significantly affect at least one basic and new technical concept of the invention.

[0067] Furthermore, the expression "consisting of" in this specification means that only the described elements, materials, or processes are present.

[0068] The term "C A -C B ” means “having A or more and B or less carbon atoms”, and the term “A to B” means “A or more and B or less”.

[0069] The term "alkyl" in the present specification refers to an organic group derived from a straight-chain or branched saturated hydrocarbon having 1 to 7, preferably 1 to 5, more preferably 1 to 3 carbon atoms, and includes, for example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl and the like.

[0070] The term "cycloalkyl" in this specification refers to a monovalent saturated carbocyclic group formed by one or more rings. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc., but are not limited thereto.

[0071] The term "alkenyl" as used 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 or 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 that are cis-oriented and trans-oriented, or alternatively E-oriented and Z-oriented.

[0072] In this specification, "normal temperature" may refer to a temperature that is not artificially temperature-regulated. For example, normal temperature may be 20°C to 40°C, 20°C to 30°C, or 23°C to 26°C.

[0073] The present invention provides a novel cyclodisilazane compound that is very useful as a precursor for producing a silicon-containing thin film, and the cyclodisilazane compound of the present invention is represented by the following Chemical Formula 1:

[0074] [Chemical Formula 1]

[0075]

[0076] In Chemical Formula 1,

[0077] R 1 is a C1-C5 alkyl group or a C3-C7 cycloalkyl group;

[0078] R 2 is a C1-C5 alkyl group, a C3-C7 cycloalkyl group, or a C1-C5 alkoxy group;

[0079] R 3 and R 4 are independently hydrogen, C1-C5 alkyl, C3-C7 cycloalkyl, or C1-C5 alkoxy; and

[0080] R 5 and R 6 are independently C2-C5 alkyl, C3-C7 cycloalkyl, or C2-C5 alkenyl.

[0081] Since the cyclodisilazane compound of the present invention has a structure in which at least one alkoxy substituent is introduced into a silicon atom in a stable four-membered ring having a Si2N2 molecular skeleton, and has a low activation energy and high thermal stability due to the alkoxy substituent introduced into the silicon atom, it has significantly improved reactivity and does not produce non-volatile by-products, and thus can easily form high-purity silicon-containing thin films at a high deposition rate. In addition, due to its excellent thermal stability, it is possible to produce films with excellent durability and high purity. In addition, since the cyclodisilazane compound of the present invention is a liquid compound at room temperature and pressure and has excellent volatility, it is easy to form good-quality silicon-containing thin films at an excellent deposition rate.

[0082] In the cyclodisilazane compound according to an exemplary embodiment, in Chemical Formula 1, R 1 Can be C1-C3 alkyl; R 2 to R 4 may be independently C1-C3 alkyl or C1-C3 alkoxy; and R 5 and R 6 They may independently be C2-C3 alkyl or C2-C3 alkenyl.

[0083] As a specific example, in Chemical Formula 1, R 1 Can be C1-C3 alkyl; R 2 to R 4 may be independently C1-C3 alkyl; and R 5 and R 6 They may independently be C2-C3 alkyl or C2-C3 alkenyl.

[0084] As a specific example, in Chemical Formula 1, R 1 Can be C1-C3 alkyl; R 2 to R 4 may be independently C1-C3 alkoxy; and R 5 and R 6 They may independently be C2-C3 alkyl or C2-C3 alkenyl.

[0085] As a specific example, in Chemical Formula 1, R 1 Can be C1-C3 alkyl; R 2 Can be C1-C3 alkyl; R 3 and R 4 may be independently C1-C3 alkyl or C1-C3 alkoxy; and R 5 and R 6 They may independently be C2-C3 alkyl or C2-C3 alkenyl.

[0086] As a specific example, in Chemical Formula 1, R 1 Can be C1-C3 alkyl; R 2 Can be C1-C3 alkoxy; R 3 and R 4 may be independently C1-C3 alkyl or C1-C3 alkoxy; and R 5 and R 6 They may independently be C2-C3 alkyl or C2-C3 alkenyl.

[0087] As a specific example, in Chemical Formula 1, R 1 Can be C1-C3 alkyl; R 2 Can be C1-C3 alkoxy; R 3 and R 4 Can be independently C1-C3 alkyl; R 5 and R 6 They may independently be C2-C3 alkyl or C2-C3 alkenyl.

[0088] More specifically, R 1 It may be methyl.

[0089] More specifically, R 2 to R 4 Each may be independently a methyl group, an ethyl group, a methoxy group, or an ethoxy group.

[0090] More specifically, R 5 and R 6 are the same as each other and may be ethyl, isopropyl, vinyl, isopropenyl, or allyl, and preferably ethyl, isopropyl, or isopropenyl.

[0091] Among the cyclic disilazane compounds according to one exemplary embodiment, the cyclic disilazane compound may be preferably represented by the following Chemical Formula 2-1 or 2-2 in terms of forming a thin film having high thermal stability and reactivity as well as high purity:

[0092] [Chemical Formula 2-1]

[0093]

[0094] [Chemical Formula 2-2]

[0095]

[0096] In Chemical Formulas 2-1 and 2-2,

[0097] R 2 to R 4 are independently C1-C3 alkyl or C1-C3 alkoxy; and

[0098] R7 It is a C2-C3 alkyl group or a C2-C3 alkenyl group.

[0099] As a specific example, in Chemical Formulas 2-1 and 2-2, R 2 to R 4 may be independently C1-C3 alkyl; and R 7 It may be a C2-C3 alkyl group or a C2-C3 alkenyl group.

[0100] As a specific example, in Chemical Formulas 2-1 and 2-2, R 2 to R 4 may be independently C1-C3 alkoxy; and R 7 It may be a C2-C3 alkyl group or a C2-C3 alkenyl group.

[0101] As a specific example, in Chemical Formulas 2-1 and 2-2, R 2 Can be C1-C3 alkyl; R 3 and R 4 may be independently C1-C3 alkyl or C1-C3 alkoxy; and R 7 It may be a C2-C3 alkyl group or a C2-C3 alkenyl group.

[0102] As a specific example, in Chemical Formulas 2-1 and 2-2, R 2 Can be C1-C3 alkoxy; R 3 and R 4 may be independently C1-C3 alkyl or C1-C3 alkoxy; and R 7 It may be a C2-C3 alkyl group or a C2-C3 alkenyl group.

[0103] The cyclodisilazane compound according to an exemplary embodiment may be selected from the following compounds, but is not limited thereto:

[0104]

[0105]

[0106] Of course, the above-mentioned cyclodisilazane compounds can be prepared by organic chemical reactions known to those skilled in the art.

[0107] In addition, the present invention provides a composition for depositing a silicon-containing thin film, comprising a cyclic disilazane compound represented by the following Chemical Formula 3, which has excellent reactivity and thermal stability and exists mainly as a liquid at room temperature, making it easy to handle:

[0108] [Chemical Formula 3]

[0109]

[0110] In Chemical Formula 3,

[0111] R 11 is a C1-C5 alkyl group or a C3-C7 cycloalkyl group;

[0112] R 12 to R 14 are independently hydrogen, C1-C5 alkyl, C3-C7 cycloalkyl, or C1-C5 alkoxy; and

[0113] R 15 and R 16 are independently C1-C5 alkyl, C3-C7 cycloalkyl, or C2-C5 alkenyl.

[0114] Since the cyclodisilazane compound contained in the composition for depositing a silicon-containing thin film of the present invention has a structure in which at least one alkoxy substituent is introduced into a silicon atom in a stable four-membered ring having a Si2N2 molecular skeleton, it exists in a liquid state at room temperature and pressure, and has low activation energy and high thermal stability due to the alkoxy substituent introduced into the silicon atom. Therefore, it has significantly improved reactivity and does not produce non-volatile by-products, and thus can easily form a high-purity silicon-containing thin film at a high deposition rate. In addition, since it can be easily stored and handled and has excellent thermal stability, it can produce a film with excellent durability and high purity.

[0115] In Chemical Formula 3 according to an exemplary embodiment, R 11 Can be C1-C3 alkyl; R 12 to R 14 may be independently hydrogen, C1-C3 alkyl, or C1-C3 alkoxy; and R 15 and R 16 They may independently be C1-C3 alkyl or C2-C3 alkenyl.

[0116] As a specific example, in Chemical Formula 3, R 11 Can be C1-C3 alkyl; R 12 to R 14 may be independently C1-C3 alkyl; and R 15 and R 16 They may independently be C1-C3 alkyl or C2-C3 alkenyl.

[0117] As a specific example, in Chemical Formula 3, R 11 Can be C1-C3 alkyl; R 12 to R 14 may be independently C1-C3 alkoxy; and R 15 and R 16They may independently be C1-C3 alkyl or C2-C3 alkenyl.

[0118] As a specific example, in Chemical Formula 3, R 11 Can be C1-C3 alkyl; R 12 Can be C1-C3 alkyl; R 13 and R 14 may be independently C1-C3 alkyl or C1-C3 alkoxy; and R 15 and R 16 They may independently be C1-C3 alkyl or C2-C3 alkenyl.

[0119] As a specific example, in Chemical Formula 3, R 11 Can be C1-C3 alkyl; R 12 Can be C1-C3 alkoxy; R 13 and R 14 may be independently C1-C3 alkyl or C1-C3 alkoxy; and R 15 and R 16 They may independently be C1-C3 alkyl or C2-C3 alkenyl.

[0120] As a specific example, in Chemical Formula 3, R 11 Can be C1-C3 alkyl; R 12 It can be hydrogen; R 13 and R 14 R may be independently hydrogen or C1-C3 alkoxy; 15 and R 16 They may independently be C1-C3 alkyl or C2-C3 alkenyl.

[0121] More specifically, R 11 It may be methyl or ethyl.

[0122] More specifically, R 12 to R 14 They may independently be hydrogen, methyl, ethyl, methoxy, or ethoxy.

[0123] More specifically, R 12 and R 13 may be independently hydrogen, methyl, ethyl, methoxy, or ethoxy, and R 14 It may be methyl, ethyl, methoxy, or ethoxy.

[0124] More specifically, R 15 and R 16 are the same as each other and may be methyl, ethyl, isopropyl, tert-butyl, vinyl, isopropenyl, or allyl, and preferably methyl, ethyl, isopropyl, tert-butyl, or isopropenyl.

[0125] Among the cyclic disilazane compounds according to one exemplary embodiment, the cyclic disilazane compound may be preferably represented by the following Chemical Formula 3-1 or 3-2 in terms of forming a thin film having high thermal stability and reactivity as well as high purity:

[0126] [Chemical Formula 3-1]

[0127]

[0128] [Chemical Formula 3-2]

[0129]

[0130] In Chemical Formulas 3-1 and 3-2,

[0131] R 12 to R 14 are independently hydrogen, C1-C3 alkyl, or C1-C3 alkoxy; and

[0132] R 17 It is a C1-C3 alkyl group or a C2-C3 alkenyl group.

[0133] As a specific example, in Chemical Formulas 3-1 and 3-2, R 12 to R 14 may be independently C1-C3 alkyl; and R 17 It may be a C1-C3 alkyl group or a C2-C3 alkenyl group.

[0134] As a specific example, in Chemical Formulas 3-1 and 3-2, R 12 to R 14 may be independently C1-C3 alkoxy; and R 17 It may be a C1-C3 alkyl group or a C2-C3 alkenyl group.

[0135] As a specific example, in Chemical Formulas 3-1 and 3-2, R 12 Can be C1-C3 alkyl; R 13 and R 14 may be independently C1-C3 alkyl or C1-C3 alkoxy; and R 17 It may be a C1-C3 alkyl group or a C2-C3 alkenyl group.

[0136] As a specific example, in Chemical Formulas 3-1 and 3-2, R 12 Can be C1-C3 alkoxy; R 13 and R 14 may be independently C1-C3 alkyl or C1-C3 alkoxy; and R 17 It may be a C1-C3 alkyl group or a C2-C3 alkenyl group.

[0137] As a specific example, in Chemical Formulas 3-1 and 3-2, R 12 It can be hydrogen; R 13 and R 14 may be independently hydrogen or C1-C3 alkoxy; and R 17 It may be a C1-C3 alkyl group or a C2-C3 alkenyl group.

[0138] In an exemplary embodiment, the cyclodisilazane compound may be selected from the following compounds, but is not limited thereto:

[0139]

[0140]

[0141] Taking into account the film formation conditions, thickness and properties of the thin film, etc., the composition for depositing a silicon-containing thin film of the present invention may contain one or more cyclodisilazane compounds of Chemical Formula 3, and contain the compounds within a content range that can be recognized by those skilled in the art. The cyclodisilazane compound is a precursor for depositing a thin film, has excellent reactivity and thermal stability, and exists mainly as a liquid at room temperature, making it easy to handle.

[0142] Furthermore, the present invention provides a method for manufacturing a silicon-containing thin film using the composition for depositing a silicon-containing thin film.

[0143] A method for manufacturing a silicon-containing thin film according to an exemplary embodiment allows for easy handling of the precursor, manufacture of the silicon-containing thin film under various conditions, and also allows for manufacture of a high-purity silicon-containing thin film with excellent step coverage at a high deposition rate by manufacturing the thin film using a composition for depositing a silicon-containing thin film containing a cyclodisilazane compound (which is liquid at room temperature, has high volatility, and has excellent thermal stability as a precursor).

[0144] The silicon-containing film according to an exemplary embodiment may be any film that can be manufactured within the scope that can be recognized by those skilled in the art, and specifically, may be a silicon oxide film (SiO2), a silicon oxycarbide film (SiOC), a silicon nitride film (SiN), a silicon oxynitride film (SiON), a silicon carbonitride film (SiCN), or a silicon carbide film (SiC), etc., and various high-quality thin films containing silicon within the scope that can be recognized by those skilled in the art can be manufactured.

[0145] The method for manufacturing a silicon-containing thin film according to an exemplary embodiment can be any method allowed within the scope that can be recognized by those skilled in the art, and can preferably be performed by the following: 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), and in terms of easier thin film deposition and excellent properties of the manufactured thin film, plasma enhanced chemical vapor deposition (PECVD) or plasma enhanced atomic layer deposition (PEALD) is preferred.

[0146] A method for manufacturing a silicon-containing thin film according to an exemplary embodiment may specifically include: a) heating a substrate installed in a chamber to a temperature of 30° C. to 700° C. and maintaining the temperature; b) contacting the substrate with a cyclodisilazane compound according to an exemplary embodiment of a composition for depositing a silicon-containing thin film according to an exemplary embodiment and allowing the compound or composition to be adsorbed onto the substrate; and c) injecting a reaction gas to deposit a silicon-containing thin film on the substrate.

[0147] Preferably, when depositing a silicon-containing thin film by plasma-enhanced atomic layer deposition (PEALD) or plasma-enhanced chemical vapor deposition (PECVD) according to an exemplary embodiment of the present invention, plasma generation may be further included after step a). In addition, in step b), the cyclodisilazane compound according to an exemplary embodiment of the composition for depositing a silicon-containing thin film according to an exemplary embodiment may be injected together with a transport gas.

[0148] In the method for manufacturing a silicon-containing thin film according to an exemplary embodiment, deposition conditions may be adjusted according to the desired structure or characteristics of the thin film, and examples of deposition conditions according to an exemplary embodiment may include the input flow rate of the cyclodisilazane compound or the composition for depositing a silicon-containing thin film containing the compound; the input flow rate of a reactive gas or a carrier gas, pressure, RF power, substrate temperature, etc. As non-limiting examples of the deposition conditions, the input flow rate of the cyclodisilazane compound or the composition for depositing a silicon-containing thin film may be adjusted to 10 cc / min to 1,000 cc / min, the flow rate of the carrier gas may be adjusted to 10 cc / min to 1,000 cc / min, the flow rate of the reactive gas may be adjusted to 1 cc / min to 1,000 cc / min, the pressure may be adjusted to 0.5 Torr to 10 Torr, the RF power may be adjusted to 200 W to 1,000 W, and the substrate temperature may be adjusted to 30° C. to 700° C., preferably 100° C. to 700° C., but the present invention is not limited thereto.

[0149] Taking into account the type of silicon-containing thin film to be manufactured, the reaction gas used in the method for manufacturing a silicon-containing thin film according to an exemplary embodiment may be any gas commonly used with a precursor, and as a specific example, may be 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 to C12 saturated or unsaturated hydrocarbons, and hydrogen, and the transport gas may be one or two or more selected from argon, helium, and nitrogen, but the present invention is not limited thereto.

[0150] The substrate used in the method for manufacturing a silicon-containing thin film according to an exemplary embodiment may 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; a glass substrate for display; a flexible plastic substrate such as polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES) and polyester; a tungsten substrate; and the like, but is not limited thereto.

[0151] In addition, in addition to forming the silicon-containing film directly on the substrate, a plurality of conductive layers, dielectric layers, insulating layers, etc. may be formed between the substrate and the silicon-containing film.

[0152] According to the present invention, by using the above-mentioned cyclodisilazane compound as a precursor, a good-quality silicon-containing thin film having high purity and durability and also having high cohesion and excellent step coverage can be produced.

[0153] Hereinafter, the present invention will be described in more detail through the following examples. Prior to this, the terms and words used in this specification and claims should not be interpreted as having ordinary meanings or dictionary meanings, but should be interpreted as having meanings and concepts that meet the technical concept of the present invention based on the principle that the inventor can appropriately define the concept of the term in order to best describe his own invention.

[0154] Therefore, the embodiments described in this specification and the configurations shown in the drawings are only the most preferred exemplary embodiments of the present invention and do not represent the entire technical spirit of the present invention. Therefore, it should be understood that there are many equivalent solutions and modified embodiments to replace them when filing this application.

[0155] In the following, all compound examples were performed using a glove box or Schlenk tube under anhydrous and inert atmosphere. 1 H NMR spectrum ( 1 The structures of the obtained cyclodisilazane compounds were analyzed using H nuclear magnetic resonance (NMR, 400 MHz Ultrashield, Buruker). Furthermore, thermogravimetric analysis (TGA, L81-II, LINSEIS) and differential scanning calorimetry (DSC) were used to measure the thermal stability, volatility, and decomposition temperature of each cyclodisilazane compound. Elementary analysis (EA) was performed using Elementar (VarioMICRICube).

[0156] In addition, all the following thin film deposition examples were performed by known plasma-enhanced atomic layer deposition (PEALD) using a commercial 200 mm showerhead style single wafer ALD tool (CN1, Atomic Premium) or by atomic layer deposition (ALD) using a 300 mm batch ALD tool (CN1, Atomic Mega).

[0157] The thickness of the deposited silicon-containing films was measured by ellipsometer (UV spectroscopic ellipsometer, Elli-SEU-am12, Ellipso technology), and the properties of the films were analyzed using an infrared spectrophotometer (Fourier transform infrared, VERTEX 70v, Bruker) and an X-ray photoelectron spectrometer (K-Alpha+, ThermoFisher Scientific). In addition, a transmission electron microscope (Tecnai F-30S-Twin, FEI) was used to analyze the step coverage of the deposited silicon-containing films.

[0158] [Example 1] Synthesis of 1-methoxy-1,3,3-trimethyl-2,4-diisopropyl-cyclodisilazane

[0159] In a flame-dried 5,000 mL Schlenk flask under anhydrous and inert atmosphere, 250 g (1.94 mol) of dichlorodimethylsilane ((CH3)2SiCl2) and 2,233 mL (19.37 mol) of n-pentane (n-C5H 12), 666.1 ml (8.14 mol) of isopropylamine ((CH ) 2 CHNH 2 ) was slowly added while maintaining the internal temperature at -20°C, followed by stirring at room temperature for 5 hours. When the stirring was completed, the reaction mixture was filtered to remove isopropylamine hydrochloride ((CH ) 2 CHNH 2 HCl), and the solvent was removed from the obtained filtrate under reduced pressure to obtain 237 g (1.36 mol) of bis(isopropylamino)dimethylsilane ((CH ) 2 Si(NHCH(CH ) 2 ) 2) (yield: 70.1%).

[0160] In a flame-dried 5,000 mL Schlenk flask under anhydrous and inert atmosphere, 270 g (1.55 mol) of the obtained bis(isopropylamino)dimethylsilane ((CH3)2Si(NHCH(CH3)2)2) and 2020.6 mL (15.47 mol) of n-hexane (n-C6H 14 ), 1,179 g (3.09 mol) of 2.62 M n-butyl lithium (n-C4H9Li) was slowly added while maintaining the internal temperature at -20°C, and then stirred at room temperature for 5 hours to prepare bis(isopropylamino)dimethylsilane lithium salt ((CH3)2Si(NLiCH(CH3)2)2). The bis(isopropylamino)dimethylsilane lithium salt ((CH3)2Si(NLiCH(CH3)2)2) prepared above was slowly added to 1000 mL of n-hexane (n-C6H9Li) while maintaining the temperature at -20°C. 14 ) and 211g (1.55mol) trimethoxymethylsilane ((CH3O)3SiCH3) in a mixed solution. After the addition was completed, the reaction solution was slowly allowed to reach room temperature and stirred at room temperature for 5 hours. After the reaction was completed, the reaction mixture was filtered to remove the methoxy lithium salt (LiOM e ), the solvent was removed from the obtained filtrate under reduced pressure, and distillation was performed under reduced pressure at 35° C. @ 0.817 Torr to obtain 280 g (1.14 mol) of 1-methoxy-1,3,3-trimethyl-2,4-diisopropyl-cyclodisilazane (C 10 H 26 N2OSi2) (yield: 73.3%).

[0161] 1 H-NMR(C6D6): δ3.47(s, 3H Si-OCH3, 3.21(m, 2H, N((CH3)2CH)2), 1.07(dd, 12H(N((CH3)2CH)2, J1=6.4Hz, J2=3.0Hz), 0.37(s, 3H, Si-CH3(OCH3)), 0.27(d, 6H, Si-(CH3)2)

[0162] 29 Si-NMR(C6D6): δ-27.0(Si(CH3)(OCH3)), -2.58(Si(CH3)2)

[0163] [Example 2] Synthesis of 1,3-dimethyl-1,3-dimethoxy-2,4-diisopropylcyclodisilazane

[0164] In a flame-dried 4,000 mL Schlenk flask under an anhydrous and inert atmosphere, 230 g (1.549 mol) of trichloro(methyl)silane (CH3SiCl3) and 2,400 ml of n-hexane as an organic solvent were added, and 183.2 g (3.09 mol) of isopropylamine ((CH3)2CHNH2) was slowly added while stirring and maintaining the temperature at -10°C. After the addition was completed, the reaction solution was slowly brought to room temperature and stirred at room temperature for 3 hours. After the stirring was completed, the white solid produced after filtration was removed and a filtrate was obtained. The solvent was removed from the filtrate under reduced pressure and 500 ml of n-hexane as an organic solvent was added to the recovered dichloro(methyl)(isopropylamino)silane (Cl2CH3SiNHCH(CH3)2), and 607 g (1.63 mol) of tert-butyllithium (t-C4H9Li)pentane (C5H9Li) with a concentration of 1.7 M was slowly added under stirring while maintaining the temperature at 65°C. 12 ) solution. After the addition was completed, the reaction solution was stirred for 12 hours. After the stirring was completed, the white solid produced was removed by filtration to obtain a filtrate, the solvent was removed from the filtrate under reduced pressure, and reduced pressure distillation was performed to obtain 147 g (0.54 mol) of 1,3-dimethyl-1,3-dichloro-2,4-diisopropylcyclodisilazane ((ClCH3SiNCH(CH3)2)2) in a yield of 70%.

[0165] In a flame-dried 4,000 mL Schlenk flask under an anhydrous and inert atmosphere, 147 g (0.54 mol) of 1,3-dimethyl-1,3-dichloro-2,4-diisopropylcyclodisilazane ((ClCH3SiNCH(CH3)2)2) prepared by the above preparation method, 2,500 ml of n-hexane and 109 g (1.08 mol) of triethylamine (NEt3) were added, and 34.72 g (1.08 mol) of methanol (CH3OH) was slowly added while maintaining the internal temperature at -15°C. After the addition was completed, the reaction solution was slowly brought to room temperature and stirred for 4 hours. After the stirring was completed, the white solid produced was removed by filtration to obtain a filtrate, the solvent was removed from the filtrate under reduced pressure, and reduced pressure distillation was performed to obtain 92 g (0.35 mol) of 1,3-dimethyl-1,3-dimethoxy-2,4-diisopropylcyclodisilazane (((CH3O)(CH3)SiNCH(CH3)2)2) with a yield of 65%.

[0166] 1 H-NMR(C6D6): δ0.33(s,3H,CH3Si), 0.35(s,3H,CH3Si), 1.08(m,12H,Si(NCH(CH3)2 ), 3.20(m, 2H, Si(NCH(CH3)2), 3.39(s, 3H, (OCH3)), 3.52(s, 3H, (OCH3)); boiling point: 214°C.

[0167] [Example 3] Synthesis of 1,1,3,3-tetramethoxy-2,4-diisopropylcyclodisilazane

[0168] In a flame-dried 10 L Schlenk flask under anhydrous and inert atmosphere, 900 g (5.30 mol) of tetrachlorosilane (SiCl4) and 3,822 g (52.97 mol) of n-pentane (n-C5H 12 ), 532.3 g (9.01 mol) of isopropylamine ((CH ) 2 CHNH ) was slowly added while maintaining the internal temperature at -20°C, followed by stirring at room temperature for 5 hours. After the stirring was completed, the reaction mixture was filtered to remove isopropylamine hydrochloride ((CH ) 2 CHNH 2 HCl), and the solvent was removed from the obtained filtrate under reduced pressure to prepare isopropylaminotrichlorosilane ((CH ) 2 CHNH)SiCl 3).

[0169] 2,776 g (32.21 mol) of n-hexane (n-C6H 14) and 775.2 g (4.03 mol) of the above-prepared isopropylaminotrichlorosilane ((CH ) 2 CHNH) SiCl 3) were added to a flask, and then 1.7 M tert-butyl lithium (C 4 H 9 Li) was slowly added over 60 minutes while refluxing at 65° C. After the reaction was completed, the reaction mixture was filtered to remove the lithium chloride salt, the solvent was removed from the obtained filtrate under reduced pressure, and reduced pressure distillation was performed at 30° C. @ 0.28 torr to prepare 1,1,3,3-tetrachloro-2,4-diisopropylcyclodisilazane ((Cl 2 SiNCH (CH 3 ) 2 ) 2 ).

[0170] 1,908 g (22.1 mol) of n-hexane (n-C6H 14 ), 345.6 g (1.11 mol) of the above-prepared 1,1,3,3-tetrachloro-2,4-diisopropylcyclodisilazane ((Cl2SiNCH(CH3)2)2) and triethylamine (NEt3) were added to a flask, and methanol (CH3OH) was slowly added while maintaining the internal temperature at -20°C. After completion of the addition, the reaction solution was slowly allowed to reach room temperature and stirred for 5 hours. After completion of the reaction, the reaction mixture was filtered to remove triethylamine hydrochloride, the solvent was removed from the obtained filtrate under reduced pressure, and then reduced pressure distillation was performed at 84°C @ 2.3 torr to obtain 175 g (0.594 mol) of 1,1,3,3-tetramethoxy-2,4-diisopropylcyclodisilazane (((CH3O)2SiNCH(CH3)2)2) as the title compound (yield: 65%).

[0171] 1 H-NMR(C6D6): δ3.53(s,12H,(CH3O)2Si), 3.23(m,2H,(CH3)2(CH)NSi), 1.12(d,12H,(CH3)2(CH)NSi)

[0172] Figure 1 and Figure 2 The results of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analysis of the cyclodisilazane compounds prepared in Examples 1 to 3 are shown, and it was confirmed therefrom that all of the cyclodisilazane compounds of the Examples exhibited high volatility, gaseous stability, and high thermal decomposition characteristics.

[0173] [Example 4] Fabrication of silicon oxide thin film by plasma enhanced atomic layer deposition (PEALD)

[0174] The 1,3-dimethyl-1,3-dimethoxy-2,4-diisopropylcyclodisilazane of Example 2 was used as a precursor to form a silicon oxide thin film by known plasma enhanced atomic layer deposition (PEALD).

[0175] A silicon substrate was used as the substrate on which the silicon oxide thin film was formed, and the silicon substrate was transferred to a deposition chamber and maintained at a constant temperature. A stainless steel bubbler-type tank filled with the precursor was also maintained at a constant temperature to maintain a constant vapor pressure of the precursor. Argon was used as the transport gas to transport the evaporated precursor into the chamber and form a film on the silicon substrate.

[0176] Specifically, a silicon substrate was maintained at 200° C., 1,3-dimethyl-1,3-dimethoxy-2,4-diisopropylcyclodisilazane (Example 2) as a precursor was filled into a stainless steel bubbler container, and the temperature was maintained at 80° C. As a reaction gas, oxygen was used with the plasma, and argon was used as an inert gas for purging purposes. The detailed method for depositing the silicon oxide thin film is shown in Table 1 below.

[0177] [Table 1]

[0178] Deposition conditions of silicon oxide thin films by plasma-enhanced atomic layer deposition

[0179]

[0180] The thickness of the film deposited in Example 4 was measured using an ellipsometer, the silicon oxide film formation was analyzed using an infrared spectrophotometer, and the composition of the silicon oxide film was analyzed using an X-ray photoelectron spectroscopy. In addition, the step coverage of the silicon oxide film was determined using a transmission electron microscope.

[0181] The specific analysis results of the silicon oxide film are shown in Table 2 below. The results of the analysis of the deposited film by infrared spectrometer are shown in Figure 3 and the results of determining the step coverage are shown in Figure 4 and Figure 5.

[0182] [Table 2]

[0183] Evaluation of Silicon Oxide Thin Film Characteristics

[0184]

[0185] It shows that the film deposited in Example 4 forms a silicon oxide film ( Figure 3 ), and as shown by the carbon content and the composition ratio of oxygen to silicon in the film in Table 2, a high-purity silicon oxide film was formed.

[0186] Furthermore, as shown in Table 2, the thin film of Example 4 was deposited at a high deposition rate. That is, the cyclodisilazane compound of the present invention can be usefully used as a precursor for depositing a thin film to form a high-purity silicon oxide thin film requiring a high deposition rate.

[0187] [Example 5] Fabrication of silicon oxide thin film by atomic layer deposition (ALD)

[0188] The 1,1,3,3-tetramethoxy-2,4-diisopropylcyclodisilazane of Example 3 was used as a precursor to form a silicon oxide thin film by known atomic layer deposition (ALD).

[0189] A silicon substrate was used as the substrate on which the silicon oxide thin film was formed, and the silicon substrate was transferred to a deposition chamber and maintained at a constant temperature. A stainless steel bubbler-type tank filled with the precursor was also maintained at a constant temperature to maintain a constant vapor pressure of the precursor. Argon was used as the transport gas to transport the evaporated precursor into the chamber and form a film on the silicon substrate.

[0190] Specifically, a silicon substrate was maintained at 650°C, 1,3,3-tetramethoxy-2,4-diisopropylcyclodisilazane (Example 3) as a precursor was filled into a stainless steel bubbler container, and the temperature was maintained at 91°C. Hydrogen and oxygen were used as reaction gases, and nitrogen was used as an inert gas for purging. The detailed method for depositing the silicon oxide thin film is shown in Table 3 below.

[0191] [Table 3]

[0192] Silicon oxide thin film deposition conditions by atomic layer deposition

[0193]

[0194] The thickness of the deposited films was measured using an ellipsometer, the silicon oxide film formation was analyzed using an infrared spectrophotometer, and the composition of the silicon oxide films was analyzed using an X-ray photoelectron spectrometer.

[0195] The specific analysis results of the silicon oxide film are shown in Table 4 below, and the results of the analysis of the deposited film by infrared spectrometer are shown in Figure 3 middle.

[0196] [Table 4]

[0197] Evaluation of silicon oxide film properties

[0198]

[0199] Depend on Figure 3 It is shown that the deposited film is a silicon oxide film, and Table 4 shows that a high-purity silicon oxide film is formed at a high deposition rate.

[0200] In the above, the present invention has been described in detail in specific parts, and it will be obvious to those skilled in the art that such specific techniques are only preferred embodiments and the scope of the present invention is not limited thereby. Therefore, the true scope of the present invention will be defined by the appended claims and their equivalents.

Claims

1. A cyclic disilazane compound represented by the following chemical formula 1: [Chemical Formula 1] In Chemical Formula 1, R 1 is a C1-C5 alkyl group or a C3-C7 cycloalkyl group; R 2 is a C1-C5 alkyl group, a C3-C7 cycloalkyl group, or a C1-C5 alkoxy group; R 3 and R 4 are independently hydrogen, C1-C5 alkyl, C3-C7 cycloalkyl, or C1-C5 alkoxy; and R 5 and R 6 are independently C2-C5 alkyl, C3-C7 cycloalkyl, or C2-C5 alkenyl.

2. The cyclodisilazane compound according to claim 1, where R 1 is a C1-C3 alkyl group; R 2 to R 4 are independently C1-C3 alkyl or C1-C3 alkoxy; and R 5 and R 6 are independently C2-C3 alkyl or C2-C3 alkenyl.

3. The cyclodisilazane compound according to claim 1, The cyclodisilazane compound is represented by the following chemical formula 2-1 or 2-2: [Chemical Formula 2-1] [Chemical Formula 2-2] In Chemical Formulas 2-1 and 2-2, R 2 to R 4 are independently C1-C3 alkyl or C1-C3 alkoxy; and R 7 It is a C2-C3 alkyl group or a C2-C3 alkenyl group.

4. The cyclic disilazane compound according to claim 1, wherein the cyclic disilazane compound is selected from the following compounds:

5. A composition for depositing a silicon-containing thin film, comprising a cyclodisilazane compound represented by the following Chemical Formula 3: [Chemical Formula 3] In Chemical Formula 3, R 11 is a C1-C5 alkyl group or a C3-C7 cycloalkyl group; R 12 to R 14 are independently hydrogen, C1-C5 alkyl, C3-C7 cycloalkyl, or C1-C5 alkoxy; and R 15 and R 16 are independently C1-C5 alkyl, C3-C7 cycloalkyl, or C2-C5 alkenyl.

6. The composition for depositing a silicon-containing thin film according to claim 5, In Chemical Formula 3, R 11 is a C1-C3 alkyl group; R 12 to R 14 are independently hydrogen, C1-C3 alkyl, or C1-C3 alkoxy; and R 15 and R 16 are independently C1-C3 alkyl or C2-C3 alkenyl.

7. The composition for depositing a silicon-containing thin film according to claim 5, wherein the cyclodisilazane 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 5 .

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

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