Cyclodisilazane compound, composition for vapor deposition of silicon-containing thin film containing the same, and method for producing silicon-containing thin film using the same

Abstract

The present invention relates to a cyclodisilazane compound, a composition for depositing a silicon-containing thin film containing the same, and a method for producing a silicon-containing thin film using the same. The cyclodisilazane compound according to the present invention is a thermally stable, highly volatile, and highly reactive compound that is liquid at room temperature and at pressures that allow easy handling. The cyclodisilazane compound can be used to form a high-purity silicon-containing thin film that has excellent physical and electrical properties by various deposition methods.

Description

[Technical Field]

[0001] The present invention relates to a novel cyclodisilazane compound, a composition for depositing a silicon-containing thin film containing the same, and a method for producing a silicon-containing thin film using the same. [Background technology]

[0002] In the semiconductor field, 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, using various deposition processes. They are used as semiconductor substrates, diffusion masks, oxidation prevention films, and dielectric films in semiconductor technologies such as microelectronic devices like RAMs (memory and logic chips), flat panel displays including thin film transistors (TFTs), and solar cells. Recently, polycrystalline silicon thin films have been used in thin film transistors (TFTs), solar cells, and their application fields are gradually diversifying.

[0003] For the deposition of high-quality silicon-containing thin films, various silicon precursors have been researched and developed, including traditional silicon precursors such as silane, disilane, and halogenated silanes, as well as aminosilanes such as butylaminosilane (BAS), bis-t-butylaminosilane (BTBAS), dimethylaminosilane (DMAS), bis-dimethylaminosilane (BDMAS), tris-dimethylaminosilane (3-DMAS), diethylaminosilane (DEAS), bis-diethylaminosilane (BDEAS), dipropylaminosilane (DPAS), and diisopropylaminosilane (DIPAS).

[0004] Representative well-known techniques for producing silicon-containing thin films include metalorganic chemical vapor deposition (MOCVD), in which a mixed gaseous silicon precursor and a reactive gas react to form a film on the surface of a substrate, or react directly on the surface to form a film, and atomic layer deposition (ALD), in which a gaseous silicon precursor is physically or chemically adsorbed on the surface of a substrate and then a reactive gas is sequentially introduced to form a film. Various thin film production technologies, such as low-pressure chemical vapor deposition (LPCVD), which is an application of these techniques, and plasma-enhanced chemical vapor deposition (PECVD) and atomic layer deposition (PEALD), which enable deposition at low temperatures, are applied to the manufacturing processes of next-generation semiconductors and display devices and are used to form ultrafine patterns and deposit thin films with uniform nanometer-level thicknesses and excellent properties.

[0005] To form high-quality silicon-containing thin films, precursors must (1) have excellent volatility with compounds that are liquid at room temperature and pressure, (2) have high thermal stability and low activation energy for the compounds themselves, making them highly reactive, (3) not produce non-volatile by-products during the thin film deposition process, and (4) be easy to handle, transport, and store.

[0006] However, due to the miniaturization of devices, the increase in aspect ratios, and the diversification of device materials resulting from the ultra-high integration of devices, there is a demand for technology to form ultra-fine thin films with uniform thin thickness and excellent electrical properties at a desired low temperature. However, problems have arisen with high-temperature processes above 600°C using conventional silicon precursors, as well as the step coverage, etching characteristics, and physical and electrical properties of the thin films.

[0007] On the other hand, even if ultrafine thin films with uniform thickness and excellent electrical properties can be formed at the low temperatures required for devices, productivity is an issue due to low thin film formation speed, and there is a need to develop new silicon precursors with improved performance. Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide a novel cyclodisilazane compound.

[0009] In particular, it is an object of the present invention to provide cyclodisilazane compounds that are liquid at room temperature and have high vapor pressure, as well as excellent volatility.

[0010] In particular, an object of the present invention is to provide a precursor compound that has good reactivity with a substrate and can form a highly reactive and stable silicon-containing thin film over a wide temperature range.

[0011] Another object of the present invention is to provide a composition for depositing a silicon-containing thin film, which contains a cyclodisilazane compound having high thermal stability and reactivity.

[0012] Another object of the present invention is to provide a method for producing a silicon-containing thin film using a cyclodisilazane compound having high thermal stability and reactivity.

[0013] Another object of the present invention is to provide a method for producing a silicon-containing thin film using the above-mentioned composition for depositing a silicon-containing thin film. [Means for solving the problem]

[0014] The present invention provides a cyclodisilazane compound represented by the following chemical formula 1: [ka] In the above Chemical Formula 1, R 1 is C1-C5 alkyl or C3-C7 cycloalkyl, R 2 is C1-C5 alkyl, C3-C7 cycloalkyl or C1-C5 alkoxy; R 3 and R 4 are each independently hydrogen, C1-C5 alkyl, C3-C7 cycloalkyl, or C1-C5 alkoxy; R 5and R 6 are each independently C2-C5 alkyl, C3-C7 cycloalkyl, or C2-C5 alkenyl.

[0015] In one embodiment, the compound is a compound represented by the formula 1, wherein R 1 is C1-C3 alkyl, and R 2 ~R 4 are each independently C1-C3 alkyl or C1-C3 alkoxy, and R 5 and R 6 may each independently be C2-C3 alkyl or C2-C3 alkenyl.

[0016] The compound according to one embodiment may be a compound represented by the following formula 2-1 or 2-2. [ka] [ka] In the above chemical formulas 2-1 and 2-2, R 2 ~R 4 are each independently C1-C3 alkyl or C1-C3 alkoxy; R 7 is C2-C3 alkyl or C2-C3 alkenyl.

[0017] The compound according to one embodiment may be at least one selected from the following structures: [ka]

[0018] The present invention also provides a composition for depositing a silicon-containing thin film, comprising a cyclodisilazane compound represented by the following Chemical Formula 3: [ka] In the above Chemical Formula 3, R 11is C1-C5 alkyl or C3-C7 cycloalkyl, R 12 ~R 14 are each independently hydrogen, C1-C5 alkyl, C3-C7 cycloalkyl, or C1-C5 alkoxy; R 15 and R 16 are each independently C1-C5 alkyl, C3-C7 cycloalkyl, or C2-C5 alkenyl.

[0019] In the silicon-containing thin film deposition composition according to one embodiment, the cyclodisilazane compound is a compound represented by the formula (3) R 11 is C1-C3 alkyl, and R 12 ~R 14 are each independently C1-C3 alkyl or C1-C3 alkoxy, and R 15 and R 16 may be compounds in which each independently is C1-C3 alkyl or C2-C3 alkenyl.

[0020] In the composition for depositing a silicon-containing thin film according to an embodiment, the cyclodisilazane compound may be at least one selected from the following structures: [ka] [ka]

[0021] The present invention also provides a method for producing a silicon-containing thin film using the above-mentioned compound.

[0022] The present invention also provides a method for producing a silicon-containing thin film using the above-mentioned composition for depositing a silicon metal-containing thin film.

[0023] In a method for manufacturing a silicon-containing thin film according to an embodiment, the manufacturing method may be performed by, but is not limited to, atomic layer deposition (ALD), chemical vapor deposition (CVD), metalorganic chemical vapor deposition (MOCVD), low-pressure chemical vapor deposition (LPCVD), plasma-enhanced chemical vapor deposition (PECVD), or plasma-enhanced atomic layer deposition (PEALD).

[0024] In the method for manufacturing a silicon-containing thin film according to an embodiment, the silicon-containing thin film may be a silicon oxide film (SiO), 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). [Effects of the Invention]

[0025] The cyclodisilazane compound according to the present invention has high volatility, excellent thermal stability, and low activation energy, making it highly reactive and therefore very useful as a precursor for silicon-containing thin film deposition. Furthermore, the cyclodisilazane compound according to the present invention exists in a liquid state at room temperature and under handleable pressures, making it easy to handle. Therefore, silicon-containing thin films prepared 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.

[0026] In addition, the composition for depositing a silicon-containing thin film according to the present invention contains a cyclodisilazane compound having high thermal stability and reactivity, and thus can produce a thin film having excellent physical and electrical properties such as excellent cohesion and step coverage at a high deposition rate, and having excellent purity and durability.

[0027] That is, according to the present invention, by using a cyclodisilazane compound as a precursor for thin film deposition, it is possible to produce a high-quality silicon-containing thin film having a high silicon content and excellent thermal stability and durability. [Brief explanation of the drawings]

[0028] [Figure 1] 1 is a thermogravimetric (TGA) graph of the cyclodisilazane compounds produced in Examples 1 to 3. [Figure 2] 1 is a differential scanning calorimetry (DSC) graph of the cyclodisilazane compounds produced in Examples 1 to 3. [Figure 3] 1 shows the results of infrared spectrophotometer analysis of silicon oxide thin films produced in Examples 4 and 5. [Figure 4] 1 is an image of step coverage of the silicon oxide thin film produced in Example 4 observed with a transmission electron microscope. DETAILED DESCRIPTION OF THE INVENTION

[0029] The present invention will be described in detail below with reference to the accompanying tables and drawings.

[0030] When drawings are described, they are provided as examples to fully convey the concept of the present invention to those skilled in the art. Therefore, the present invention is not limited to the drawings shown, and may be embodied in other forms, and the drawings may be exaggerated to clarify the concept of the present invention.

[0031] In this case, unless otherwise defined, the technical and scientific terms used have the meanings that are commonly understood by a person of ordinary skill in the art to which the present invention belongs, and in the following description and accompanying drawings, descriptions of known functions and configurations that may obscure the gist of the present invention will be omitted.

[0032] Also, as used herein, the singular forms "a," "an," and "the" can be intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0033] Furthermore, units used in this specification without any special mention are based on weight, and as an example, the unit of % or ratio means % by weight or weight ratio, and % by weight means the weight % that any one component of the total composition occupies in the composition unless otherwise defined.

[0034] Numerical ranges used herein include lower and upper limits, and all values ​​within that range, increments logically derived from the shape and width of the defined range, all values ​​defined therein, and all possible combinations of upper and lower limits of numerical ranges defined in different ways.

[0035] Also, in this specification, the term "comprising" is an open-ended term having the same meaning as expressions such as "comprising," "containing," "having," or "characterized by," and does not exclude further unrecited elements, materials, or steps.

[0036] Also, as used herein, the term "substantially" means that other elements, materials, or steps not listed together with a particular element, material, or step may be present in an amount that does not unacceptably affect at least one basic and novel technical idea of ​​the invention.

[0037] Also, as used herein, the term "comprises" means that only the stated elements, materials or steps are present.

[0038] The term "C" used herein A -C B " means "the number of carbon atoms is A or more and B or less," and the term "A to B" means "A or more and B or less."

[0039] As used herein, the term "alkyl" means an organic radical derived from a straight or branched chain saturated hydrocarbon having from 1 to 7 carbon atoms, preferably 1 to 5, and more preferably 1 to 3 carbon atoms, and includes, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, and the like.

[0040] As used herein, the term "cycloalkyl" refers to a monovalent saturated carbocyclic radical composed of one or more rings. Examples of cycloalkyl radicals include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.

[0041] The term "alkenyl," alone or as part of another group described herein, refers to a straight- or branched-chain hydrocarbon radical containing 2 to 7 carbon atoms and one or more carbon-to-carbon double bonds. Preferred alkenyl radicals are lower alkenyl radicals having 2 to 5 carbon atoms. More preferred alkenyl radicals are radicals having 2 to 3 carbon atoms. Alkenyl groups may also be substituted at any available point of attachment. Examples of alkenyl radicals include vinyl, propenyl, allyl, butenyl, and 4-methylbutenyl. The term alkenyl embraces radicals having cis and trans orientations, or alternatively, E and Z orientations.

[0042] In this specification, "normal temperature" may mean a temperature in a state where the temperature is not artificially adjusted, and for example, the normal temperature may be 20°C to 40°C, or 20°C to 30°C, or 23°C to 26°C.

[0043] 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.

[0044] [ka]

[0045] In the above Chemical Formula 1, R 1 is C1-C5 alkyl or C3-C7 cycloalkyl, R 2 is C1-C5 alkyl, C3-C7 cycloalkyl or C1-C5 alkoxy; R 3 and R 4 are each independently hydrogen, C1-C5 alkyl, C3-C7 cycloalkyl, or C1-C5 alkoxy; R 5 and R6 are each independently C2-C5 alkyl, C3-C7 cycloalkyl, or C2-C5 alkenyl.

[0046] The cyclodisilazane compound of the present invention has a structure in which at least one alkoxy group is introduced to the silicon atom of a stable four-membered ring having a SiN molecular skeleton. The alkoxy group introduced to the silicon atom provides lower activation energy and high thermal stability, significantly improving reactivity and enabling the easy formation of high-purity silicon-containing thin films at a high deposition rate without producing non-volatile by-products. Furthermore, the compound has excellent thermal stability, allowing the production of thin films with high durability and purity. Furthermore, the cyclodisilazane compound of the present invention has excellent volatility as a liquid compound at room temperature and atmospheric pressure, facilitating the formation of high-quality silicon-containing thin films at a high deposition rate.

[0047] In one embodiment of the cyclodisilazane compound, in Formula 1, R 1 is C1-C3 alkyl, and R 2 ~R 4 are each independently C1-C3 alkyl or C1-C3 alkoxy, and R 5 and R 6 may each independently be C2-C3 alkyl or C2-C3 alkenyl.

[0048] As a specific example, in the above-mentioned chemical formula 1, R 1 is C1-C3 alkyl, and R 2 ~R 4 are each independently C1-C3 alkyl, and R 5 and R 6 may each independently be C2-C3 alkyl or C2-C3 alkenyl.

[0049] As a specific example, in the above-mentioned chemical formula 1, R 1 is C1-C3 alkyl, and R 2 ~R 4 are each independently C1-C3 alkoxy, and R5 and R 6 may each independently be C2-C3 alkyl or C2-C3 alkenyl.

[0050] As a specific example, in the above-mentioned chemical formula 1, R 1 is C1-C3 alkyl, and R 2 is C1-C3 alkyl, and R 3 and R 4 are each independently C1-C3 alkyl or C1-C3 alkoxy, and R 5 and R 6 may each independently be C2-C3 alkyl or C2-C3 alkenyl.

[0051] As a specific example, in the above-mentioned chemical formula 1, R 1 is C1-C3 alkyl, and R 2 is C1-C3 alkoxy, and R 3 and R 4 are each independently C1-C3 alkyl or C1-C3 alkoxy, and R 5 and R 6 may each independently be C2-C3 alkyl or C2-C3 alkenyl.

[0052] As a specific example, in the above-mentioned chemical formula 1, R 1 is C1-C3 alkyl, and R 2 is C1-C3 alkoxy, and R 3 and R 4 are each independently C1-C3 alkyl, and R 5 and R 6 may each independently be C2-C3 alkyl or C2-C3 alkenyl.

[0053] More specifically, the R 1 may be methyl.

[0054] More specifically, the R 2 ~R 4may each independently be methyl, ethyl, methoxy, or ethoxy.

[0055] More specifically, the R 5 and R 6 are the same as each other and may be ethyl, isopropyl, vinyl, isopropenyl or allyl, preferably ethyl, isopropyl or isopropenyl.

[0056] In the cyclodisilazane compound according to one embodiment, in terms of high thermal stability, reactivity, and ability to form a thin film with high purity, the cyclodisilazane compound may be preferably represented by the following Chemical Formula 2-1 or 2-2.

[0057] [ka] [ka] In the above chemical formulas 2-1 and 2-2, R 2 ~R 4 are each independently C1-C3 alkyl or C1-C3 alkoxy; R 7 is C2-C3 alkyl or C2-C3 alkenyl.

[0058] As a specific example, in the chemical formulas 2-1 and 2-2, R 2 ~R 4 are each independently C1-C3 alkyl, and R 7 may be C2-C3 alkyl or C2-C3 alkenyl.

[0059] As a specific example, in the chemical formulas 2-1 and 2-2, R 2 ~R 4 are each independently C1-C3 alkoxy, and R 7 may be C2-C3 alkyl or C2-C3 alkenyl.

[0060] As a specific example, in the chemical formulas 2-1 and 2-2, R 2 is C1-C3 alkyl, and R 3 and R 4 are each independently C1-C3 alkyl or C1-C3 alkoxy, and R 7 may be C2-C3 alkyl or C2-C3 alkenyl.

[0061] As a specific example, in the chemical formulas 2-1 and 2-2, R 2 is C1-C3 alkoxy, and R 3 and R 4 are each independently C1-C3 alkyl or C1-C3 alkoxy, and R 7 may be C2-C3 alkyl or C2-C3 alkenyl.

[0062] The cyclodisilazane compound according to one embodiment may be selected from, but is not limited to, the following compounds: [ka]

[0063] It goes without saying that the above-mentioned cyclodisilazane compounds can be prepared by conventional organic chemical reactions known to those skilled in the art.

[0064] The present invention also provides a composition for silicon-containing thin film deposition, which contains a cyclodisilazane compound represented by the following Chemical Formula 3, which has excellent reactivity and thermal stability, is mostly liquid at room temperature, and is easy to handle:

[0065] [ka]

[0066] In the above Chemical Formula 3, R 11 is C1-C5 alkyl or C3-C7 cycloalkyl, R 12 ~R 14are each independently hydrogen, C1-C5 alkyl, C3-C7 cycloalkyl, or C1-C5 alkoxy; R 15 and R 16 are each independently C1-C5 alkyl, C3-C7 cycloalkyl, or C2-C5 alkenyl.

[0067] The cyclodisilazane compound contained in the silicon-containing thin film deposition composition of the present invention has a structure in which at least one alkoxy group is introduced to the silicon atom of a stable four-membered ring having a SiN molecular skeleton, and exists in a liquid state at room temperature and atmospheric pressure. The alkoxy group introduced to the silicon atom provides lower activation energy and high thermal stability, thereby significantly improving reactivity and enabling the easy formation of high-purity silicon-containing thin films at a high deposition rate without producing non-volatile by-products. Furthermore, the composition is easy to store and handle, has excellent thermal stability, and can produce thin films with high durability and excellent purity.

[0068] In one embodiment, in Formula 3, R 11 is C1-C3 alkyl, and R 12 ~R 14 are each independently C1-C3 alkyl or C1-C3 alkoxy, and R 15 and R 16 may each independently be C1-C3 alkyl or C2-C3 alkenyl.

[0069] As a specific example, in the above-mentioned chemical formula 3, R 11 is C1-C3 alkyl, and R 12 ~R 14 are each independently C1-C3 alkyl, and R 15 and R 16 may each independently be C1-C3 alkyl or C2-C3 alkenyl.

[0070] As a specific example, in the above-mentioned chemical formula 3, R 11 is C1-C3 alkyl, and R 12~R 14 are each independently C1-C3 alkoxy, and R 15 and R 16 may each independently be C1-C3 alkyl or C2-C3 alkenyl.

[0071] As a specific example, in the above-mentioned chemical formula 3, R 11 is C1-C3 alkyl, and R 12 is C1-C3 alkyl, and R 13 and R 14 are each independently C1-C3 alkyl or C1-C3 alkoxy, and R 15 and R 16 may each independently be C1-C3 alkyl or C2-C3 alkenyl.

[0072] As a specific example, in the above-mentioned chemical formula 3, R 11 is C1-C3 alkyl, and R 12 is C1-C3 alkoxy, and R 13 and R 14 are each independently C1-C3 alkyl or C1-C3 alkoxy, and R 15 and R 16 may each independently be C1-C3 alkyl or C2-C3 alkenyl.

[0073] As a specific example, in the above-mentioned chemical formula 3, R 11 is C1-C3 alkyl, and R 12 is hydrogen and R 13 and R 14 are each independently hydrogen or C1-C3 alkoxy, and R 15 and R 16 may each independently be C1-C3 alkyl or C2-C3 alkenyl.

[0074] More specifically, the R 11 may be methyl or ethyl.

[0075] More specifically, the R 12~R 14 may each independently be hydrogen, methyl, ethyl, methoxy, or ethoxy.

[0076] More specifically, the R 12 and R 13 are each independently hydrogen, methyl, ethyl, methoxy, or ethoxy; R 14 may be methyl, ethyl, methoxy or ethoxy.

[0077] More specifically, the R 15 and R 16 are the same as each other and may be methyl, ethyl, isopropyl, t-butyl, vinyl, isopropenyl or allyl, preferably methyl, ethyl, isopropyl, t-butyl or isopropenyl.

[0078] In the cyclodisilazane compound according to one embodiment, in terms of high thermal stability, reactivity, and ability to form a thin film with high purity, the cyclodisilazane compound may be preferably represented by the following Chemical Formula 3-1 or 3-2.

[0079] [ka]

[0080] [ka]

[0081] In the above chemical formulas 3-1 and 3-2, R 12 ~R 14 are each independently hydrogen, C1-C3 alkyl, or C1-C3 alkoxy; R 17 is C1-C3 alkyl or C2-C3 alkenyl.

[0082] As a specific example, in the chemical formulas 3-1 and 3-2, R 12 ~R14 are each independently C1-C3 alkyl, and R 17 may be C1-C3 alkyl or C2-C3 alkenyl.

[0083] As a specific example, in the chemical formulas 3-1 and 3-2, R 12 ~R 14 are each independently C1-C3 alkoxy, and R 17 may be C1-C3 alkyl or C2-C3 alkenyl.

[0084] As a specific example, in the chemical formulas 3-1 and 3-2, R 12 is C1-C3 alkyl, and R 13 and R 14 are each independently C1-C3 alkyl or C1-C3 alkoxy, and R 17 may be C1-C3 alkyl or C2-C3 alkenyl.

[0085] As a specific example, in the chemical formulas 3-1 and 3-2, R 12 is C1-C3 alkoxy, and R 13 and R 14 are each independently C1-C3 alkyl or C1-C3 alkoxy, and R 17 may be C1-C3 alkyl or C2-C3 alkenyl.

[0086] As a specific example, in the chemical formulas 3-1 and 3-2, R 12 is hydrogen and R 13 and R 14 are each independently hydrogen or C1-C3 alkoxy, and R 17 may be C1-C3 alkyl or C2-C3 alkenyl.

[0087] In one embodiment, the cyclodisilazane compound may be selected from, but is not limited to, the following compounds: [ka] [ka]

[0088] The silicon-containing thin film deposition composition of the present invention may contain one or more cyclodisilazane compounds of Formula 3, which are precursors for thin film deposition and have excellent reactivity and thermal stability, and are easy to handle since most of them exist as liquids at room temperature. The content of the cyclodisilazane compounds may be within a range that can be recognized by those skilled in the art, taking into consideration the thin film deposition conditions, the thickness, and properties of the thin film, etc.

[0089] The present invention also provides a method for producing a silicon-containing thin film using the above-mentioned composition for depositing a silicon-containing thin film.

[0090] According to an embodiment, a method for manufacturing a silicon-containing thin film uses a composition for depositing a silicon-containing thin film, the composition including the cyclodisilazane compound, which is liquid at room temperature, highly volatile, and has excellent thermal stability, as a precursor. This makes it possible to easily handle the precursor, manufacture a silicon-containing thin film under various conditions, and manufacture a high-purity silicon-containing thin film with a high deposition rate and excellent step coverage.

[0091] The silicon-containing thin film according to an embodiment may be any thin film that can be manufactured within the scope of recognition by a person skilled in the art in this technical field, and specifically may be a silicon oxide film (SiO), 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. In addition, various high-quality thin films containing silicon can be manufactured within the scope of recognition by a person skilled in the art.

[0092] A method for manufacturing a silicon-containing thin film according to an embodiment may be any method known to those skilled in the art, but may be preferably performed by atomic layer deposition (ALD), chemical vapor deposition (CVD), metalorganic chemical vapor deposition (MOCVD), low-pressure chemical vapor deposition (LPCVD), plasma-enhanced chemical vapor deposition (PECVD), or plasma-enhanced atomic layer deposition (PEALD). In view of easier thin film deposition and superior properties of the manufactured thin film, plasma-enhanced chemical vapor deposition (PEALD) or plasma-enhanced chemical vapor deposition (PECVD) is preferred.

[0093] The method for producing a silicon-containing thin film according to an embodiment may specifically include the steps of: a) heating and maintaining a temperature of a substrate mounted in a chamber at 30 to 700°C; b) contacting the substrate with a cyclodisilazane compound according to an embodiment or a composition for depositing a silicon-containing thin film according to an embodiment, and allowing the compound to be adsorbed onto the substrate; and c) injecting a reaction gas to deposit a silicon-containing thin film on the substrate.

[0094] Preferably, when plasma-enhanced atomic layer deposition (PEALD) or plasma-enhanced chemical vapor deposition (PECVD) is performed on the silicon-containing thin film according to an embodiment of the present invention, a step of generating plasma may be further included after step a), and in step b), the cyclodisilazane compound according to an embodiment or the composition for depositing a silicon-containing thin film according to an embodiment may be injected together with a carrier gas.

[0095] In an embodiment of a method for producing a silicon-containing thin film, deposition conditions may be adjusted depending on the desired structure or properties of the thin film. Examples of deposition conditions include the feed rate of the cyclodisilazane compound or the silicon-containing thin film deposition composition containing the same, the feed rate of the reactive gas and the carrier gas, pressure, RF power, and substrate temperature. Non-limiting examples of such deposition conditions include the feed rate of the cyclodisilazane compound or the silicon-containing thin film deposition composition being 10 to 1000 cc / min, the carrier gas being 10 to 1000 cc / min, the reactive gas being 1 to 1000 cc / min, the pressure being 0.5 to 10 torr, the RF power being 200 to 1000 W, and the substrate temperature being 30 to 700°C, preferably 100 to 700°C, but are not limited thereto.

[0096] The reactive gas used in the method for manufacturing a silicon-containing thin film according to an embodiment may be any gas typically used with a precursor, taking into consideration the material of the silicon-containing thin film to be manufactured. Specific examples of the reactive gas include oxygen (O), ozone (O), distilled water (H), hydrogen peroxide (H), nitric oxide (NO), nitrous oxide (N), nitrogen dioxide (NO), ammonia (NH), nitrogen (N), hydrazine (N), amine, diamine, carbon monoxide (CO), carbon dioxide (CO), C1-C12 saturated or unsaturated hydrocarbons, and hydrogen. The carrier gas may be, but is not limited to, one or more selected from argon, helium, and nitrogen.

[0097] The substrate used in the method for manufacturing a silicon-containing thin film according to an embodiment may be, but is not limited to, a substrate including one or more semiconductor materials selected from the group consisting of Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP, a silicon-on-insulator (SOI) substrate, a quartz substrate, a glass substrate for a display, a flexible plastic substrate such as polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES), polyester, or a tungsten substrate.

[0098] In addition, the silicon-containing thin film may be formed directly on the substrate, or multiple conductive layers, dielectric layers, or insulating layers may be formed between the substrate and the silicon-containing thin film.

[0099] According to the present invention, by using the above-mentioned cyclodisilazane compound as a precursor, it is possible to produce a high-quality silicon-containing thin film that not only has high purity and durability but also has high cohesion and excellent step coverage.

[0100] The present invention will be described in more detail below with reference to the following examples. Before that, the terms and words used in the specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted as meanings and concepts that are consistent with the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concepts of terms to best describe his / her invention.

[0101] Therefore, the examples described in this specification and the configurations illustrated in the drawings are merely the most preferred embodiments of the present invention and do not represent all of the technical ideas of the present invention, so it should be understood that there are various equivalents and modifications that can be used instead at the time of this application.

[0102] All of the following examples of compounds were carried out in an anhydrous and inert atmosphere using a glove box or a Schlenk flask. The structure of the obtained cyclodisilazane compound is: 1 H NMR spectrum ( 1 Analysis was performed by H Nuclear Magnetic Resonance (NMR, 400 MHz Ultrashield, Buruker). Thermogravimetric analysis (TGA, L81-II, LINSEIS) and differential scanning calorimeter (DSC) were also performed to measure the thermal stability, volatility, and decomposition temperature of each cyclodisilazane compound. Elemental analysis (EA) was performed using an Elementar (Vario MICRI Cube).

[0103] In addition, all thin film deposition examples below are performed using a commercially available showerhead-type 200 mm single wafer type ALD equipment (CN1, Atomic Premium) to carry out known plasma-enhanced atomic layer deposition (PEALD) or a 300 mm batch type ALD equipment (CN1, Atomic Premium) to carry out atomic layer deposition (ALD).

[0104] The deposited silicon-containing thin films were measured for thickness using a UV Spectroscopic Ellipsometer (Elli-SEU-am12, Ellipso Technology), and their properties were analyzed using a Fourier transform infrared spectrophotometer (VERTEX 70v, Bruker) and an X-ray Photoelectron Spectrometer (K-Alpha+, ThermoFisher Scientific). The step coverage of the deposited silicon-containing thin films was also analyzed using a transmission electron microscope (Tecnai F-30 S-Twin, FEI).

[0105] [Example 1] Synthesis of 1-methoxy-1,3,3-trimethyl-2,4-diisopropyl-cyclodisilazane In a flame-dried 5,000 mL Schlenk flask under an anhydrous and inert atmosphere, add 250 g (1.94 mol) of dichlorodimethylsilane ((CH3)2SiCl2) and n-pentane (n-CH5H 12 After adding 2,233 mL (19.37 mol) of isopropylamine ((CH3)2CHNH2) 666.1 mL (8.14 mol) slowly while maintaining the internal temperature at -20°C, the mixture was stirred at room temperature for 5 hours. After stirring was completed, the reaction mixture was filtered to remove isopropylamine hydrochloride ((CH3)2CHNH2 HCl). The solvent was removed from the resulting filtrate under reduced pressure to obtain 237 g (1.36 mol) of bis(isopropylamino)dimethylsilane ((CH3)2Si(NHCH(CH3)2)2) (70.1% yield).

[0106] In a flame-dried 5,000 mL Schlenk flask under an anhydrous and inert atmosphere, 270 g (1.55 mol) of the obtained bis(isopropylamino)dimethylsilane ((CH3)2Si(NHCH(CH3)2)2) and n-hexane (n-CH6H 14)2020.6 mL (15.47 mol) was added, and while maintaining the internal temperature at -20 °C, 2.62 M n-butyllithium (n-C4H9Li)1,179 (3.09 mol) was gradually added, and the mixture was stirred at room temperature for 5 hours to produce bis(isopropylamino)dimethylsilane lithium salt ((CH3)2Si(NLiCH(CH3)2)2). n-hexane (n-C6H 14 To a mixed solution of 1000 mL of bis(isopropylamino)dimethylsilane ((CH3O)3SiCH3)2 and 11 g (1.55 mol) of trimethoxymethylsilane ((CHO)3SiCH3), the bis(isopropylamino)dimethylsilane lithium salt ((CH3)2Si(NLiCH(CH3)2)2) prepared above was gradually added while maintaining the temperature at -20°C. After the addition was completed, the reaction solution was gradually warmed to room temperature and stirred at room temperature for 5 hours. After the reaction was completed, the reaction mixture was filtered to remove the methoxylithium salt (LiOMe). The solvent was removed from the resulting filtrate under reduced pressure, and the resulting solution was then distilled under reduced pressure at 35°C @ 0.817 torr to obtain the title compound, 1-methoxy-1,3,3-trimethyl-2,4-diisopropyl-cyclodisilazane (C 10 H 26 280 g (1.14 mol) of N2OSi2 was obtained (yield 73.3%).

[0107] 1 H-NMR (C6D6): δ 3.47 (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) 29 Si-NMR (C6D6) : δ -27.0 (Si(CH3)(OCH3)), -2.58 (Si(CH3)2)

[0108] [Example 2] Synthesis of 1,3-dimethyl-1,3-dimethoxy-2,4-diisopropyl cyclodisilazane A flame-dried 4,000 mL Schlenk flask was charged with 230 g (1.549 mol) of trichloro(methyl)silane (CH3SiCl3) and 2,400 mL of n-hexane, an organic solvent, under an anhydrous and inert atmosphere. While stirring, 183.2 g (3.09 mol) of isopropylamine ((CH3)2CHNH2) was gradually added while maintaining the temperature at -10°C. After the addition was completed, the reaction solution was gradually warmed to room temperature and stirred at room temperature for 3 hours. After stirring was completed, the resulting white solid was removed by filtration, and the filtrate was obtained. The solvent was removed from the filtrate under reduced pressure, and the recovered dichloro(methyl)(isopropylamino)silane (Cl2CH3SiNHCH(CH3)2) was added to 500 mL of n-hexane, an organic solvent, and the mixture was stirred while adding 1.7 M t-butyllithium (t-C4H9Li) in pentane (C5H 12 A solution of 607 g (1.63 mol) of 1,3-dimethyl-1,3-dichloro-2,4-diisopropylcyclodisilazane ((ClCH3SiNCH(CH3)2)2)2) was gradually added while maintaining the temperature at 65°C. After the addition was complete, the reaction solution was stirred for 12 hours. After the stirring was complete, the resulting white solid was removed by filtration, and the filtrate was obtained. The solvent was removed from this filtrate under reduced pressure, and 147 g (0.54 mol) of 1,3-dimethyl-1,3-dichloro-2,4-diisopropylcyclodisilazane ((ClCH3SiNCH(CH3)2)2) was obtained in a 70% yield.

[0109] In a flame-dried 4000 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 then 4.72 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 gradually warmed to room temperature and stirred for 4 hours. After stirring was completed, the resulting white solid was removed by filtration, and the filtrate was obtained. The solvent was removed from this filtrate under reduced pressure, and 92 g (0.35 mol) of 1,3-dimethyl-1,3-dimethoxy-2,4-diisopropylcyclodisilazane (((CHO)(CH)SiNCH(CH))) was obtained in a yield of 65%.

[0110] 1 H-NMR (C6D6) : δ 0.33 (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℃.

[0111] [Example 3] Synthesis of 1,1,3,3-tetramethoxy-2,4-diisopropyl cyclodisilazane In a flame-dried 10 L Schlenk flask under an anhydrous and inert atmosphere, add 900 g (5.30 mol) of tetrachlorosilane (SiCl) and n-pentane (n-CH). 123,822g (52.97mol) of isopropylamine ((CH3)2CHNH2) was added, and while maintaining the internal temperature at -20°C, 532.3g (9.01mol) of isopropylamine ((CH3)2CHNH2) was gradually added, followed by stirring at room temperature for 5 hours. Once stirring was complete, the reaction mixture was filtered to remove isopropylamine hydrochloride ((CH3)2CHNH2·HCl), and the solvent was removed from the resulting filtrate under reduced pressure to produce isopropylaminotrichlorosilane ((CH3)2CHNH)SiCl3).

[0112] n-Hexane (n-CH 14 2,776 g (32.21 mol) of tetrachlorosilane ((CH3)2CHNH)SiCl3) and 775.2 g (4.03 mol) of the isopropylaminotrichlorosilane prepared above were placed in a flask and refluxed at 65°C. 1.7 M t-butyllithium (C4H9Li) was added gradually over 60 minutes. After the reaction was complete, the reaction mixture was filtered to remove the lithium chloride salt. The solvent was removed from the resulting filtrate under reduced pressure, followed by vacuum distillation at 30°C @ 0.28 torr to produce 1,1,3,3-tetrachloro-2,4-diisopropylcyclodisilazane ((Cl2SiNCH(CH3)2)2).

[0113] n-Hexane (n-CH 14 1,908 g (22.1 mol) of 1,1,3,3-tetrachloro-2,4-diisopropylcyclodisilazane ((ClSiNCH(CH))) prepared above, 345.6 g (1.11 mol) of 1,1,3,3-tetrachloro-2,4-diisopropylcyclodisilazane ((ClSiNCH(CH))), and triethylamine (NEt) were added, and methanol (CHOH) was slowly added while maintaining the internal temperature at -20°C. After the addition was complete, the reaction solution was gradually warmed to room temperature and stirred for 5 hours. After the reaction was complete, the reaction mixture was filtered to remove triethylamine hydrochloride. The solvent was removed from the resulting filtrate under reduced pressure and then distilled under reduced pressure at 84°C @ 2.3 torr to obtain 175 g (0.594 mol) of the title compound, 1,1,3,3-tetramethoxy-2,4-diisopropylcyclodisilazane ((CHO)SiNCH(CH)). The yield was 65%.

[0114] 1H-NMR (C6D6): δ 3.53 (s, 12H, (CH3O)2Si), 3.23 (m, 2H, (CH3)2(CH)NSi), 1.12 (d, 12H, (CH3)2(CH)NSi)

[0115] 1 and 2 show the results of thermogravimetry (TGA) and differential scanning calorimetry (DSC) analysis of the cyclodisilazane compounds prepared in Examples 1 to 3. From these, it was confirmed that the cyclodisilazane compounds of the Examples all exhibited high volatility, gas phase stability, and high thermal decomposition properties.

[0116] [Example 4] Fabrication of silicon oxide thin films by plasma-enhanced atomic layer deposition (PEALD) Using 1,3-dimethyl-1,3-dimethoxy-2,4-diisopropylcyclodisilazane of Example 2 as a precursor, a silicon oxide thin film was formed by the known plasma-enhanced atomic layer deposition (PEALD) method.

[0117] A silicon substrate was used as the substrate on which the silicon oxide thin film was formed. The silicon substrate was transferred into a deposition chamber and maintained at a predetermined temperature. A stainless steel bubbler-type canister filled with the precursor was also maintained at a predetermined temperature to maintain a constant vapor pressure of the precursor. The vaporized precursor was transferred into the chamber using argon gas as a carrier gas and deposited on the silicon substrate.

[0118] Specifically, the silicon substrate was maintained at 200°C, and the precursor 1,3-dimethyl-1,3-dimethoxy-2,4-diisopropylcyclodisilazane (Example 2) was filled into a stainless steel bubbler vessel and maintained at 80°C. Oxygen was used as the reactive gas along with the plasma, and argon, an inert gas, was used for purging. The specific silicon oxide thin film deposition method is shown in Table 1 below.

[0119] [Table 1]

[0120] The thickness of the thin film deposited in Example 4 was measured using an ellipsometer, the silicon oxide thin film formation was analyzed using an infrared spectrophotometer, the composition of the silicon oxide thin film was analyzed using an X-ray photoelectron spectrometer, and the step coverage of the silicon oxide thin film was confirmed using a transmission electron microscope.

[0121] Table 2 below shows the specific analysis results of the silicon oxide thin film, Figure 3 shows the results of analyzing the deposited thin film using an infrared spectrometer, and Figures 4 and 5 show the results of checking the step coverage.

[0122] [Table 2]

[0123] The thin film deposited in Example 4 was shown to have formed a silicon oxide thin film (Figure 3), and the carbon content and the composition ratio of oxygen and silicon in the thin film in Table 2 indicate that a high-purity silicon oxide thin film was formed.

[0124] Furthermore, it can be seen from Table 2 that the thin film of Example 4 was deposited at a high deposition rate. That is, the cyclodisilazane compound of the present invention can be useful as a precursor for thin film deposition to form high-purity silicon oxide thin films that require a high deposition rate.

[0125] [Example 5] Fabrication of silicon oxide thin film by atomic layer deposition (ALD) Using 1,1,3,3-tetramethoxy-2,4-diisopropylcyclodisilazane of Example 3 as a precursor, a silicon oxide thin film was formed by the known atomic layer deposition (ALD) method.

[0126] A silicon substrate was used as the substrate on which the silicon oxide thin film was formed. The silicon substrate was transferred into a deposition chamber and maintained at a predetermined temperature. A stainless steel bubbler-type canister filled with the precursor was also maintained at a predetermined temperature to maintain a constant vapor pressure of the precursor. The vaporized precursor was transferred into the chamber using argon gas as a carrier gas and deposited on the silicon substrate.

[0127] Specifically, the silicon substrate was maintained at 650°C, and the precursor 1,3,3-tetramethoxy-2,4-diisopropylcyclodisilazane (Example 3) was filled into a stainless steel bubbler vessel and maintained at 91°C. Hydrogen and oxygen were used as reaction gases, and nitrogen, an inert gas, was used for purging. A specific silicon oxide thin film deposition method is shown in Table 3 below.

[0128] [Table 3]

[0129] The thickness of the deposited thin film was measured using an ellipsometer, the silicon oxide thin film formation was analyzed using an infrared spectrophotometer, and the composition of the silicon oxide thin film was analyzed using an X-ray photoelectron spectrometer.

[0130] Table 4 below shows the specific analysis results of the silicon oxide thin film, and FIG. 3 shows the results of analyzing the deposited thin film using an infrared spectrometer.

[0131] [Table 4]

[0132] From FIG. 3, it can be seen that the deposited thin film is a silicon oxide thin film, and from Table 4, it can be seen that a high purity silicon oxide thin film is formed at a high deposition rate.

[0133] Although the specific details of the present invention have been described above, it is clear to those skilled in the art that these specific details are merely preferred embodiments and do not limit the scope of the present invention. Therefore, the true scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A cyclodisilazane compound represented by the following chemical formula 1. 【Chemistry 1】 In the above Chemical Formula 1, R １ is C1-C5 alkyl or C3-C7 cycloalkyl; R ２ is C1-C5 alkyl, C3-C7 cycloalkyl or C1-C5 alkoxy; R ３ and R ４ are each independently hydrogen, C1-C5 alkyl, C3-C7 cycloalkyl, or C1-C5 alkoxy; R ５ and R ６ are each independently C2-C5 alkyl, C3-C7 cycloalkyl, or C2-C5 alkenyl.

2. The R １ is C1-C3 alkyl, R ２ ~R ４ are each independently C1-C3 alkyl or C1-C3 alkoxy; R ５ and R ６ are each independently a C2-C3 alkyl or a C2-C3 alkenyl.

3. The cyclodisilazane compound according to claim 1, wherein the cyclodisilazane compound is represented by the following chemical formula 2-1 or 2-2: 【Chemistry 2】 【Transformation 3】 In the chemical formulas 2-1 and 2-2, R ２ ~R ４ are each independently C1-C3 alkyl or C1-C3 alkoxy; R ７ is a C2-C3 alkyl or a C2-C3 alkenyl.

4. 2. The cyclodisilazane compound according to claim 1, which is selected from the following compounds: 【Chemistry 4】

5. A composition for depositing a silicon-containing thin film, comprising a cyclodisilazane compound represented by the following chemical formula 3: 【Transformation 5】 In the above Chemical Formula 3, R １１ is C1-C5 alkyl or C3-C7 cycloalkyl; R １２ ~R １４ are each independently hydrogen, C1-C5 alkyl, C3-C7 cycloalkyl, or C1-C5 alkoxy; R １５ and R １６ are each independently C1-C5 alkyl, C3-C7 cycloalkyl, or C2-C5 alkenyl.

6. In the above chemical formula 3, R １１ is C1-C3 alkyl, R １２ ~R １４ are each independently hydrogen, C1-C3 alkyl, or C1-C3 alkoxy; R １５ and R １６ are each 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: 【Chemistry 6(1)】 【Chemistry 6(2)】

8. A method for producing a silicon-containing thin film using the silicon-containing thin film deposition composition according to claim 5.

9. 9. The method for producing the silicon-containing thin film of claim 8, which is carried out by atomic layer deposition (ALD), chemical vapor deposition (CVD), metalorganic 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 silicon-containing thin film is a silicon oxide film (SiO ２ 9. The method for producing a silicon-containing thin film according to claim 8, wherein the silicon-containing thin film is 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).

Images