Method for forming silicon-containing films, and compositions and silicon precursor compounds used therefor

Abstract

Using a silicon-containing film-forming composition containing a silicon precursor compound represented by Formula 1, a silicon-containing film, including a silicon-containing oxide film or a silicon-containing composite metal oxide film, can be efficiently formed at a high temperature of at least 600°C. The silicon-containing film can be controlled to have a desired thickness and composition, and can be formed with excellent coverage and uniformity even on substrates with complex shapes. JPEG2026502448000041.jpg34149 [In formula 1, R1 and R2 are each independently selected from the group consisting of hydrogen and a linear or branched C1-C4 alkyl group, or R1 and R2 are bonded directly or indirectly to each other to form a substituted or unsubstituted C4-C9 cyclic group, with the proviso that the C4-C9 cyclic group contains one or two nitrogen (N) atoms and zero to two oxygen (O) atoms.]

Description

[Technical Field]

[0001] The present invention relates to a method for forming a silicon-containing film, and a composition and a silicon precursor compound used therein. Specifically, the present invention relates to a method for forming a silicon-containing film at a high temperature of 600°C or higher using a silicon-containing film-forming composition containing a silicon precursor compound having a specific structure, a silicon-containing film prepared thereby, and a composition and a silicon precursor compound used therein. [Background technology]

[0002] Silicon-containing films are one of the essential thin films for driving non-semiconductor devices such as logic devices and semiconductors such as DRAM, flash memory, resistive random access memory (ReRAM), and phase-change memory (PCRAM).

[0003] Silicon-containing oxide films have high deposition rates, while silicon-containing nitride films have low deposition rates. For various applications, there is a demand for silicon-containing films that can be selectively deposited only in desired locations.

[0004] Furthermore, as products having complex shapes such as high aspect ratios and three-dimensional structures are being developed in a variety of memory and non-memory fields, there is a demand for silicon-containing film-forming compositions that are suitable for process temperatures for various application fields, can overcome high step ratios, and contain silicon precursor compounds that can be used for atomic layer deposition (ALD).

[0005] In particular, it is important to exhibit self-limiting film growth properties in order to overcome the step ratios that may be caused by the increasing integration and miniaturization of devices.

[0006] Therefore, there is a need to develop a film-forming composition containing a silicon precursor compound that has self-limiting film growth properties at high temperatures of 600°C or higher, is suitable for ALD, can form uniform and dense films, and has stress resistance; and a method for forming a silicon-containing film using the same. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Korean Patent No. 10-0734393 Summary of the Invention technical challenges

[0008] The technical problem to be solved by the present invention is to provide a method for forming a silicon-containing film at a high temperature of 600°C or higher using a silicon-containing film-forming composition containing a silicon precursor compound having a specific structure, and a silicon-containing film prepared thereby.

[0009] Another technical problem that the present invention aims to solve is to provide a silicon precursor compound having a specific structure.

[0010] Another technical problem that the present invention aims to solve is to provide a method for preparing silicon precursor compounds.

[0011] Another technical problem to be solved by the present invention is to provide a composition for forming a silicon-containing film, which contains a silicon precursor compound.

[0012] However, the problems to be solved by the present invention are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

[0013] The present invention provides a method for forming a silicon-containing film, the method comprising depositing the silicon-containing film using a silicon-containing film-forming composition comprising a silicon precursor compound represented by Formula 1.

[0014] [ka]

[0015] In Formula 1, R1 and R2 are each independently selected from the group consisting of hydrogen and a linear or branched C1-C4 alkyl group, or R1 and R2 are bonded directly or indirectly to each other to form a substituted or unsubstituted C4-C9 cyclic group, where the C4-C9 cyclic group contains one or two nitrogen (N) atoms and zero to two oxygen (O) atoms.

[0016] Furthermore, the present invention provides a silicon-containing film-forming composition that contains a silicon precursor compound represented by the above formula 1 and is used to deposit a silicon-containing film.

[0017] Furthermore, the present invention provides the use of a silicon precursor compound represented by the above formula 1 for forming a silicon-containing film.

[0018] Additionally, the present invention provides a silicon-containing film formed by the method of forming a silicon-containing film.

[0019] Furthermore, the present invention provides a silicon precursor compound represented by Formula 0 or Formula 1.

[0020] [ka]

[0021] [ka]

[0022] In Formula 1, R1 and R2 are each independently selected from the group consisting of hydrogen and a linear or branched C1-C4 alkyl group, or R1 and R2 are bonded directly or indirectly to each other to form a substituted or unsubstituted C4-C9 cyclic group, provided that the C4-C9 cyclic group contains one or two nitrogen (N) atoms and zero to two oxygen (O) atoms.

[0023] A method for forming a silicon-containing film according to an embodiment of the present invention can efficiently form a silicon-containing film including at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing complex metal oxide film by using a silicon-containing film-forming composition containing a silicon precursor compound having a specific structure at a high temperature of 600° C. or higher. It is possible to accurately control the desired film thickness and composition, and to form a uniform silicon-containing film with excellent coverage even on substrates with complex shapes.

[0024] In particular, the method for forming a silicon-containing film of the present invention can be applied to various fields such as memory devices, logic devices, display devices, and moisture barriers for organic light-emitting diode (OLED) devices, and a film of a desired thickness can be obtained at a high temperature of 600°C or higher during film deposition. Therefore, the method can be very effectively used in electronic devices that require excellent film properties and coverage. [Brief explanation of the drawings]

[0025] [Figure 1] 1 is a graph showing the deposition characteristics of silicon-containing oxide films at temperatures of 600°C to 850°C when silicon-containing films are deposited using compositions for forming silicon-containing films containing the silicon precursor compounds of Examples 1 and 3 of the present invention and Comparative Examples 1 and 2. [Figure 2] 1 is a graph showing the results of secondary ion mass spectrometry (SIMS) of silicon-containing oxide films deposited at a temperature of 750°C using silicon-containing film-forming compositions containing the silicon precursor compounds of Example 3 of the present invention and Comparative Example 1. [Figure 3] 1 is a transmission electron microscope (TEM) image confirming step coverage upon deposition on a patterned wafer at 750° C. using silicon-containing film-forming compositions containing the silicon precursor compounds of Examples 1 and 3 of the present invention and Comparative Example 1, respectively. [Figure 4]1 is a transmission electron microscope (TEM) image confirming step coverage upon deposition on a patterned wafer at 650° C. using silicon-containing film-forming compositions containing the silicon precursor compounds of Example 3 of the present invention and Comparative Example 1, respectively. DETAILED DESCRIPTION OF THE INVENTION

[0026] The present application will now be described in more detail.

[0027] The advantages and features of the present invention, as well as methods for achieving these advantages and features, will become apparent from and elucidated with reference to the embodiments described below. However, the present invention is not limited to the embodiments described below, and may be embodied in various different forms. These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. The present invention is defined solely by the claims.

[0028] Furthermore, when an element is referred to as being formed "on" another element, this does not mean that the element is directly formed "on" the other element, but also that there are other elements interposed between the elements.

[0029] In this specification, when a part is referred to as "comprising" an element, unless otherwise indicated, it should be understood that the part does not exclude other elements, but may include other elements as well.

[0030] All numbers and expressions relating to amounts of components, reaction conditions, and the like used herein should be understood to be modified by the term "about" unless otherwise indicated.

[0031] As used herein, the terms "film" and "thin film" refer to both "film" and "thin film," respectively, unless otherwise specified.

[0032] As used herein, the term "alkyl" or "alkyl group" includes straight-chain or branched alkyl groups and all possible isomers thereof. For example, alkyl or alkyl groups include, but are not limited to, methyl (Me), ethyl (Et), normal propyl (nPr), isopropyl (iPr), normal butyl (nBu), isobutyl (iBu), tert-butyl (tert-Bu, tBu), sec-butyl (secBu), and the like, as well as their isomers.

[0033] [Method for forming silicon-containing films] According to an embodiment of the present invention, there is provided a method for forming a silicon-containing film, the method comprising depositing a silicon-containing film using a silicon-containing film-forming composition comprising a silicon precursor compound represented by Formula 1.

[0034] [ka]

[0035] In Formula 1, R1 and R2 are each independently selected from the group consisting of hydrogen and a linear or branched C1-C4 alkyl group, or R1 and R2 are bonded directly or indirectly to each other to form a substituted or unsubstituted C4-C9 cyclic group, where the C4-C9 cyclic group contains one or two nitrogen (N) atoms and zero to two oxygen (O) atoms.

[0036] As an example, R1 and R2 in Formula 1 can each independently be selected from the group consisting of hydrogen, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a tert-butyl group, and a sec-butyl group.

[0037] As another example, in Formula 1, R1 and R2 (together with the N atom to which R1 and R2 are bonded) are bonded directly or indirectly to each other to form a substituted or unsubstituted C4-C9 cyclic group, the cyclic group containing one or two nitrogen (N) atoms and zero to two oxygen (O) atoms. Specific examples of C4-C9 cyclic groups include azetidinyl, pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, and azepanyl. The C4-C9 cyclic group may have one or more, for example, one to three, substituents. The substituent that the C4-C9 cyclic group may have may be, for example, at least one selected from the group consisting of a C1-C6 alkyl group, a halogen atom (F, Cl, Br, and I), a hydroxyl group (OH), and a C1-C6 alkoxy, but is not limited thereto.

[0038] Specifically, the method for forming a silicon-containing film may include depositing a silicon-containing film on a substrate by chemical vapor deposition (CVD) or atomic layer deposition (ALD) using a silicon-containing film-forming composition containing a silicon precursor compound represented by Formula 1. The silicon-containing film may include at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing complex metal oxide film. The deposition may be performed at a temperature of 600°C or higher, specifically 600°C to 850°C.

[0039] In some embodiments, the silicon-containing film can be formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD) at temperatures between 600°C and 850°C.

[0040] According to a method for forming a silicon-containing film according to an embodiment of the present invention, it is possible to efficiently form a silicon-containing film comprising at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing complex metal oxide film at a high temperature of 600° C. or higher using a silicon-containing film-forming composition containing a silicon precursor compound having a specific structure represented by the above formula 1. It is possible to accurately control the desired film thickness and composition, and to form a uniform silicon-containing film with excellent coverage even on substrates with complex shapes.

[0041] In particular, the method for forming a silicon-containing film of the present invention can be applied to various fields such as moisture barriers for memory devices, logic devices, display devices, and organic light-emitting diode (OLED) devices, and is technically significant in that a film of a desired thickness can be obtained at a high temperature of 600°C or higher during film deposition.

[0042] Furthermore, the present invention provides a silicon-containing film-forming composition that contains a silicon precursor compound represented by the above formula 1 and is used to deposit a silicon-containing film by chemical vapor deposition (CVD) or atomic layer deposition (ALD) at a temperature of 600°C or higher, wherein the silicon-containing film comprises at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing complex metal oxide film.

[0043] Specifically, in the method for forming a silicon-containing film, the formation of the silicon-containing film may include depositing the silicon-containing film on a substrate (board) using a silicon-containing film-forming composition containing a silicon precursor compound represented by the above formula 1.

[0044] The substrate can be, but is not limited to, a silicon semiconductor wafer, a compound semiconductor wafer, or a plastic substrate (PI, PET, or PES). Furthermore, substrates with holes or grooves may be used, and porous substrates with large surface areas may be used.

[0045] In particular, at temperatures above 600°C, specifically in the range of 600°C to 850°C, a silicon-containing film having a uniform thickness of several nanometers (nm) to several micrometers (μm) can be formed on a substrate having a pattern (groove) on its surface, a porous substrate, or even a plastic substrate; the excellent effect of uniformly forming a silicon-containing film covering the deepest surface of the fine pattern (groove) and an upper surface having at least one fine irregularity (groove) having an aspect ratio of 1 or more, for example, about 1 to 50 or more, and a width of 1 μm or less, for example, about 1 μm to 10 nm or less, can be achieved. For example, a silicon-containing film can be formed on a substrate having at least one irregularity having an aspect ratio of 1 or more and a width of 1 μm or less.

[0046] The deposition of the silicon-containing film may be performed using any method and apparatus known in the art to which the present invention pertains, and may optionally be performed using one or more additional reactive gases, etc.

[0047] The deposition of silicon-containing films can be carried out by CVD, such as metalorganic chemical vapor deposition (MOCVD), or ALD, which can be carried out using deposition equipment, deposition conditions, and reactive gases known in the art.

[0048] Specifically, a substrate is placed in a reaction chamber, and then a silicon-containing film-forming composition containing a silicon precursor compound is transferred onto the substrate using a transport gas or a dilution gas, and a silicon-containing film is deposited at a deposition temperature of 600°C or higher, specifically 600°C to 850°C.

[0049] The deposition temperature range described above allows this method to be applied to memory devices, logic devices, and display devices. The wide process temperature range allows this method to be applied to a variety of fields. In particular, the use of a silicon-containing film-forming composition containing a silicon precursor compound that is stress-resistant and can form a dense film at high temperatures allows for easy deposition within the deposition temperature range described above.

[0050] As the transport gas or dilution gas, it is preferable to use a mixed gas of at least one selected from the group consisting of argon (Ar), nitrogen (N2), helium (He), and hydrogen (H2).

[0051] Furthermore, the method for forming a silicon-containing film may include supplying a silicon precursor compound to the reaction chamber using at least one method selected from the group consisting of a bubbling method, a liquid delivery system (LDS) method, a vapor flow control (VFC) method, and a bypass method.

[0052] Specifically, the method for delivering the silicon precursor compound to the reaction chamber may be at least one method selected from the group consisting of a bubbling method in which a silicon-containing film-forming composition containing the silicon precursor compound is forcibly vaporized using a transport gas or a dilution gas; a liquid delivery system (LDS) method in which the composition is supplied in a liquid phase at room temperature and vaporized through a vaporizer; a vapor flow control (VFC) method in which the precursor is directly supplied using its vapor pressure; and a bypass method for vaporization by heating.

[0053] For example, when the vapor pressure is high, the vapor flow rate control method can be used.When the vapor pressure is low, the bypass method of heating the container to vaporize, or the bubbling method of using argon (Ar) or nitrogen (N) gas can be used to supply the silicon-containing film-forming composition comprising silicon precursor compound to the reaction chamber.

[0054] In some embodiments, the step of delivering the silicon precursor compound to the reaction chamber may be performed using a transport or diluent gas at a temperature range of room temperature to 150° C. and at 0.1 to 10 Torr.

[0055] More specifically, the delivery method includes a bubbling method or a bypass method, and the bubbling method may be performed using a transport gas or a dilution gas at a temperature range of room temperature to 150° C. and 0.1 Torr to 10 Torr, or the bypass method may be performed using a vapor pressure of 0.1 Torr to 1.5 Torr at a temperature range of room temperature to 100° C. For example, the silicon-containing film-forming composition containing a silicon precursor compound may be supplied to a reaction chamber using a transport gas or a dilution gas at a temperature range of room temperature to 100° C. and 0.1 Torr to 10 Torr.

[0056] Furthermore, to vaporize the silicon-containing film-forming composition containing the precursor compound, for example, argon (Ar) or nitrogen (N2) gas can be used to transport the composition. Alternatively, thermal energy or plasma can be used, or a bias can be applied to the substrate during deposition.

[0057] Meanwhile, according to the method for forming a silicon-containing film, to deposit at least one silicon-containing film selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film, at least one selected from the group consisting of water vapor (HO), oxygen (O), oxygen plasma (O plasma), hydrogen peroxide (HO), and ozone (O) may be used during deposition.

[0058] The at least one silicon-containing film selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film is, for example, HfSiO x , ZrSiO x , TiSiO x , HfAlO x , ZrAlSiO x , TiAlSiO x , ZrHfSiO x , ZrHfAlSiO x , SiC, and SiCO, where x may be 1 to 3.

[0059] The silicon-containing film-forming composition containing the silicon precursor compound represented by the above formula 1 will be described in detail below.

[0060] [Silicon-containing film-forming composition] The present invention provides a silicon-containing film-forming composition comprising a silicon precursor compound represented by formula 1 above.

[0061] Specifically, the silicon-containing film-forming composition includes a silicon precursor compound represented by the above formula 1 and can be used to deposit a silicon-containing film by chemical vapor deposition (CVD) or atomic layer deposition (ALD) at a temperature of 600°C or higher, and the silicon-containing film includes at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing complex metal oxide film.

[0062] The silicon-containing film-forming composition according to an embodiment of the present invention contains a silicon precursor compound having a specific structure represented by Formula 1 above, and therefore is capable of forming a uniform silicon-containing film, specifically a silicon-containing oxide film, with excellent coverage even on a substrate having a complex shape.

[0063] In particular, the above formula 1 has a structure in which an amine having an alkyl group, which has excellent reactivity with a silicon surface and is thermally stable, is bonded, and has a structure containing three silicon atoms. Therefore, formula 1 may be more advantageous for forming a stable silicon-containing film at a high deposition rate at a high temperature of about 600°C to 850°C.

[0064] Specifically, in the silicon precursor compound represented by Formula 1, first, the amine represented by -NR1R2 in the structure has excellent reactivity with surfaces such as Si, Si-OH, and Si-O, which is advantageous for the formation of silicon-containing oxide films. Second, the presence of multiple thermally stable Si and CH3 bonds in the structure allows the silicon precursor to form stable films at temperatures above 600°C without rapid decomposition, making it suitable for 3D NAND flash memory processes that require uniform and dense silicon-containing films with excellent coverage at high temperatures. Third, this structure has a significantly larger GPC in SiO2 ALD than that of conventional silicon precursor compounds containing three Si atoms, making it suitable for 3D NAND flash memory processes that form thick SiO2 films at high temperatures.

[0065] Specifically, R1 and R2 are each independently selected from the group consisting of hydrogen and a linear or branched C1-C4 alkyl group, or R1 and R2 are bonded directly or indirectly to each other to form a substituted or unsubstituted C4-C9 cyclic group, the C4-C9 cyclic group containing 1 or 2 nitrogen (N) atoms and 0-2 oxygen (O) atoms.

[0066] The silicon precursor compound may include one or more selected from the group consisting of compounds represented by formulas 1-1 to 1-10.

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] According to some embodiments of the present invention, when deposition is carried out by ALD using a silicon-containing film-forming composition, it may have a deposition rate per cycle (GPC) of 1.5 to 4.5 Å / cycle of ALD gas supply in the temperature range of 600°C to 850°C.

[0078] Specifically, when a SiO2 film is formed by ALD using a silicon-containing film-forming composition, the deposition rate per cycle (GPC) of the ALD gas supply can be 1.5 to 4.5 Å / cycle in the temperature range of 600°C to 850°C.

[0079] For example, when deposition is carried out by ALD using a silicon-containing film-forming composition, it is possible to achieve a deposition rate per cycle (GPC) of ALD gas supply of, for example, 1.5-4.0 Å / cycle, 1.7-4.0 Å / cycle, 2.0-4.0 Å / cycle, 1.5-3.5 Å / cycle, 1.7-3.5 Å / cycle, 1.5-3.0 Å / cycle, or 2.0-3.0 Å / cycle at a temperature range of 600°C to 850°C, e.g., 800°C.

[0080] When a silicon-containing film is formed using a silicon-containing film-forming composition according to an embodiment of the present invention, the composition can be controlled to achieve a desired film thickness and a desired silicon content, and a uniform film with excellent coverage can be formed even on a substrate having a pattern (groove) on its surface, a porous substrate, a plastic substrate, or a substrate having a complex shape with a three-dimensional structure, thereby providing a high-quality silicon-containing film.

[0081] Furthermore, using the silicon-containing film-forming composition, it is possible to efficiently form, on a substrate by CVD or ALD, a silicon-containing film including at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film, as well as at least one selected from the group consisting of a silicon-containing nitride film, a silicon-containing carbide film, and a silicon-containing composite metal film.

[0082] In particular, according to an embodiment of the present invention, when a silicon-containing film comprising at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film is formed on a substrate by ALD using a silicon-containing film-forming composition, a film having a desired thickness and a uniform thickness can be obtained at high temperatures of 600°C or higher, and there are significant advantages in that a high-quality, pure silicon-containing film with a low film shrinkage rate and wet etching rate at high temperatures and few impurities can be formed.

[0083] [Silicon precursor compounds] The present invention provides silicon precursor compounds represented by Formula 0 or Formula 1.

[0084] [ka]

[0085] [ka]

[0086] In Formula 1, R1 and R2 are each independently selected from the group consisting of hydrogen and a linear or branched C1-C4 alkyl group, or R1 and R2 are bonded directly or indirectly to each other to form a substituted or unsubstituted C4-C9 cyclic group, where the C4-C9 cyclic group contains one or two nitrogen (N) atoms and zero to two oxygen (O) atoms.

[0087] The compounds of Formula 0 and Formula 1 can be used to form silicon-containing films.

[0088] Specifically, the compound of Formula 0 can be used to prepare the compound of Formula 1, and the silicon-containing film-forming composition including the compound of Formula 1 can be used to deposit a silicon-containing film.

[0089] Accordingly, the present invention provides the use of a silicon precursor compound represented by Formula 1 above for forming a silicon-containing film.

[0090] The silicon precursor compound may be selected from the group consisting of compounds represented by formulas 1-1 to 1-10 above.

[0091] Silicon-containing films can be formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD) at temperatures between 600°C and 850°C.

[0092] Furthermore, when a SiO2 film is formed by atomic layer deposition (ALD) using a silicon precursor compound, the film formation rate per cycle of ALD gas supply is 1.5 to 4.5 Å / cycle in the temperature range of 600 °C to 850 °C.

[0093] Furthermore, the silicon-containing film may be formed by a method including the step of supplying a silicon precursor compound to a reaction chamber using at least one method selected from the group consisting of a bubbling method, a liquid delivery system (LDS) method, a vapor flow control (VFC) method, and a bypass method.

[0094] Furthermore, the step of supplying the silicon precursor compound to the reaction chamber may be performed using a transport gas or a dilution gas at a temperature range of room temperature to 150° C. and 0.1 to 10 Torr.

[0095] Additionally, silicon precursor compounds are used to deposit silicon-containing films. During deposition, thermal energy or plasma can be used, or a bias can be applied to the substrate.

[0096] Furthermore, the silicon-containing film may comprise at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing complex metal oxide film, a silicon precursor compound may be used in the deposition of the silicon-containing film, and at least one selected from the group consisting of water vapor (HO), oxygen (O), oxygen plasma (O plasma), hydrogen peroxide (HO), and ozone (O) may be used during the deposition.

[0097] Furthermore, the silicon-containing film can be formed in a thickness range of 1 nm to 500 nm.

[0098] Additionally, the silicon-containing film can be formed on a substrate having at least one irregularity with an aspect ratio of 1 or greater and a width of 1 μm or less.

[0099] [Method for preparing silicon precursor compounds] Meanwhile, the silicon precursor compound represented by the above formula 1 can be prepared by various methods.

[0100] A method for preparing a silicon precursor compound (Formula 1) according to an embodiment of the present invention may include the steps of subjecting a hexamethyldisilazane metal salt represented by the following Formula A to a halide-hexamethyldisilazane substitution reaction with a dihalide silicon precursor compound represented by the following Formula B to form a compound represented by the following Formula C, and subjecting the compound represented by the following Formula C to a halide-amine substitution reaction with a dialkylamine or cyclic amine represented by the following Formula D to form a compound represented by the following Formula 1:

[0101] [ka]

[0102] In Reaction Scheme 1, M1 is an alkali metal (Li or Na). R1 ​​and R2 are each independently selected from the group consisting of hydrogen and a linear or branched C1-C4 alkyl group, or R1 and R2 are bonded directly or indirectly to each other to form a substituted or unsubstituted C4-C9 cyclic group, where the C4-C9 cyclic group contains one or two nitrogen (N) atoms and zero to two oxygen (O) atoms. X1 and X2 are each independently a halogen atom and Cl, Br, or I.

[0103] According to another example, the silicon precursor compound of formula 1 above can be obtained by using a silicon precursor compound of formula 0.

[0104] [ka]

[0105] Specifically, the silicon precursor compound represented by the above formula 1 can be easily synthesized by reacting the silicon precursor compound represented by the above formula 0 with a secondary amine.

[0106] The silicon precursor compound of formula 0 is commercially available and can be easily synthesized using dichlorosilane (SiH2Cl2) and hexamethyldisilazane (1,1,1,3,3,3-hexamethyldisilazane) as inexpensive raw materials. The silicon precursor compound of formula 0 can be used to prepare the silicon precursor compound of formula 1.

[0107] Referring to Reaction Scheme 1 above, when preparing the silicon precursor compound (Formula 1), 0.5 to 2 moles of a dihalide silicon precursor compound (Formula B) are added to a hexamethyldisilazane metal salt (Formula A) at a low temperature (approximately -30°C to -5°C) to carry out a first substitution reaction between the halide and hexamethyldisilazane. Next, the metal halide salt contained in the reaction product as a reaction by-product is removed using a filter, and the remaining product is purified to obtain a compound represented by Formula C. Subsequently, 1 to 3 moles of a dialkylamine or cyclic amine (Formula D) are added to the compound represented by Formula C at a low temperature (approximately -30°C to -5°C) to carry out a substitution reaction between the halide and amine. Next, the dialkylamine halide salt or cyclic amine halide salt contained in the reaction product as a reaction by-product is removed using a filter, and the remaining product is purified to obtain the silicon precursor compound represented by Formula 1.

[0108] The first and second halide-amine substitution reactions can be carried out in a solvent at 0° C. to 30° C., specifically 20° C. to 30° C., for example, at room temperature for 2 to 30 hours.

[0109] Furthermore, the solvent may include at least one selected from the group consisting of alkanes having 5 to 8 carbon atoms, toluene, ether, tetrahydrofuran, and mono- to tetra-ethylene glycol dimethyl ether.

[0110] According to some embodiments of the present invention, the silicon precursor compound can be used to obtain a silicon-containing film-forming composition comprising the silicon precursor compound.

[0111] [Silicon-containing film] According to one embodiment of the present invention, there is provided a silicon-containing film formed using a silicon-containing film-forming composition containing a silicon precursor compound represented by Formula 1 above.

[0112] Specifically, a silicon-containing film formed using a silicon-containing film-forming composition containing a silicon precursor compound represented by formula 1 above is provided.

[0113] The silicon-containing film can have a thickness of several nanometers (nm) to several micrometers (μm) and can be applied in various ways depending on the application. Specifically, the silicon-containing film can be formed to a thickness in the range of 1 nm to 500 nm.

[0114] The silicon-containing film can be formed on a substrate (board).

[0115] The substrate is as described above.

[0116] The silicon-containing film may include at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing complex metal oxide film.

[0117] Furthermore, by using a silicon-containing film-forming composition containing a silicon precursor compound represented by formula 1, it is possible to efficiently form at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film.

[0118] Furthermore, since the silicon-containing film is prepared by using a silicon-containing film-forming composition containing a silicon precursor compound having excellent thermal stability, it has a low shrinkage rate even at high temperatures of 600°C or higher, for example, 600°C to 850°C, and is characterized by having a low wet etching rate (Å / s).

[0119] Specifically, the silicon-containing film has a shrinkage (S) of 5.0% or less, as expressed in Equation 1 below: 750 ). Shrinkage rate (S 750 ,%)=(AB) / A×100 [Equation 1]

[0120] In Equation 1, A is the initial thickness (Å) of the silicon-containing film formed by ALD at 750°C, and B is the thickness (Å) of the silicon-containing film formed by ALD at 750°C after aging at 750°C for 60 minutes in an argon (Ar) atmosphere.

[0121] The shrinkage rate (S) of silicon-containing films is given by Equation 1. 750 ) can be, for example, 4.8% or less, 4.5% or less, 4.4% or less, 4.0% or less, 3.9% or less, 3.8% or less, 3.5% or less, 3.4% or less, 3.3% or less, 3.2% or less, 3.0% or less, 2.5% or less, 2.0% or less, 1.5% or less, 1.2% or less, 1.1% or less, or 1.0% or less. Specifically, the shrinkage ratio (S 750 ) may be 4.8% to 0.5%, 3.5% to 0.5%, 3.0% to 0.5%, or 2.5% to 0.5%.

[0122] The shrinkage rate (S 750 ), it can be advantageous for forming a uniform and dense silicon-containing film.

[0123] On the other hand, if a silicon-containing film is formed to a thickness of 500 Å by deposition at 750° C. and the thickness of the silicon-containing film is measured with an ellipsometer before and after exposure to an etching solution of 1% dilute hydrofluoric acid, the wet etching rate (Å / s) of the silicon-containing film, as expressed by the following Equation 2, may be 4.0 Å / s or less. Wet etch rate (Å / s) = change in etched thickness (ΔE, Å) / 30 s [Equation 2]

[0124] The change in etch thickness (ΔE) can be expressed by the following equation 2-1: Change in etching thickness (ΔE, Å) = E A -E B [Equation 2-1]

[0125] In equation 2-1, E Ais the initial thickness (Å) of the silicon-containing film formed by ALD at 750 °C, and E B is the thickness (Å) of the silicon-containing film formed by ALD at 750° C. after etching in a 1% dilute HF solution for 30 seconds.

[0126] In Equation 2, "s" means seconds.

[0127] The wet etch rate (Å / s) of the silicon-containing film represented by Equation 2 can be, for example, 3.8 Å / s or less, 3.5 Å / s or less, 3.2 Å / s or less, 3.0 Å / s or less, less than 2.9 Å / s, 2.8 Å / s or less, 2.7 Å / s or less, 2.6 Å / s or less, 2.55 Å / s or less, 2.51 Å / s or less, 2.5 Å / s or less, 2.45 Å / s or less, 2.4 Å / s or less, 2.2 Å / s or less, 2.1 Å / s or less, 2.0 Å / s or less, 1.5 Å / s or less, 1.0 Å / s or less, 0.95 Å / s or less, 0.5 Å / s or less, 0.1 Å / s or less, 0.05 Å / s or less, or 0.03 Å / s or less.

[0128] Specifically, the wet etch rate (Å / s) of the silicon-containing film represented by Equation 2 can be 3.8 Å / s to 0.5 Å / s, 3.5 Å / s to 0.5 Å / s, 3.0 Å / s to 0.5 Å / s, 2.8 Å / s to 0.5 Å / s, 2.7 Å / s to 0.5 Å / s, 2.6 Å / s to 0.5 Å / s, 2.51 Å / s to 0.5 Å / s, 2.5 Å / s to 0.5 Å / s, 2.1 Å / s to 0.5 Å / s, 2.0 Å / s to 0.5 Å / s, 1.5 Å / s to 0.5 Å / s, 1.2 Å / s to 0.5 Å / s, or 1.0 Å / s to 0.5 Å / s.

[0129] When the silicon-containing film has a wet etching rate (Å / s) that satisfies the above range, it can be advantageous for forming a uniform and dense silicon-containing film.

[0130] Additionally, silicon-containing films may have excellent step coverage.

[0131] Specifically, a silicon-containing film is deposited on a substrate having a stepped groove pattern as shown in Figure 3 and then analyzed using a transmission electron microscope (TEM). The step coverage can then be calculated as shown in Equation 3 below. Step coverage (%) = B / A × 100 (%) [Equation 3]

[0132] In Equation 3, A is the thickness (Å) measured at the top of the groove and B is the thickness (Å) measured at the bottom of the groove.

[0133] The silicon-containing film may have a step coverage (%) of, for example, 80% or more, 82% or more, 85% or more, 90% or more, 92% or more, 92.5% or more, 92.9% or more, 93% or more, 95% or more, or 96% or more. As a specific example, the step coverage (%) of the silicon-containing film may be 80% to 99%, 85% to 99%, or 95% to 99%.

[0134] When the silicon-containing film has a step coverage (%) that satisfies the above range, a high step ratio and fine thickness control are possible, and as a result, it can be advantageously used to manufacture various semiconductor devices such as DRAMs and 3D NAND flash memories. [Example]

[0135] The present invention will be described in detail below with reference to examples. The following examples are provided to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0136] <Example 0> Preparation of chloro-(hexamethyldisilyl)aminosilane: [ClSiH2{N(SiMe3)2}] [ka]

[0137] In a 20-liter round-bottom flask, approximately 910.02 g (2.5 M, approximately 3.267 mol) of n-butyllithium hexane solution (n-BuLi in n-hexane) was mixed with approximately 4,000 ml of anhydrous hexane. Approximately 575.27 g (approximately 3.564 mol) of hexamethyldisilazane (1,1,1,3,3,3-hexamethyldisilazane) was added at approximately -20°C, followed by gradual warming to room temperature with stirring and subsequent stirring for 4 hours. Approximately 330 g (approximately 3.267 mol) of dichlorosilane was slowly added to the thus-formed lithium (1,1,1,3,3,3-hexamethyldisilazane) salt at -20°C to -10°C, followed by gradual warming to room temperature with stirring and subsequent stirring for 17 hours. After the reaction was completed, the salts formed during the reaction were removed by filtration, and the solvent and volatile by-products were removed by vacuum distillation to obtain 637 g (yield: 95.00%) of chloro(hexamethyldisilyl)aminosilane [ClSiH{N(SiMe)}] as a colorless liquid compound represented by Formula 0, which was used in Examples 1 to 5.

[0138] 1 H-NMR(C6D6):δ0.165(N-Si-CH3,s,18H),δ5.148(Si-H2,s,2H)

[0139] Example 1 Preparation of a silicon-containing film-forming composition containing pyrrolidinyl-(hexamethyldisilyl)aminosilane and pyrrolidinyl-(hexamethyldisilyl)aminosilane [(CH2CH2CH2CH2N)SiH2{N(SiMe3)2}] [ka]

[0140] In a 2-liter round-bottom flask, approximately 18.73 g (0.083 mol) of chloro(hexamethyldisilyl)aminosilane obtained in Example 0 above was mixed with approximately 1,000 ml of anhydrous hexane. Approximately 12.97 g (approximately 0.182 mol) of pyrrolidine was added thereto at approximately -20°C, and the mixture was gradually warmed to room temperature with stirring and continued to stir for 18 hours. Upon completion of the reaction, the salt formed during the reaction was removed by filtration, and the solvent and volatile by-products were removed by vacuum distillation to obtain 75 g (74.29% yield) of pyrrolidinyl(hexamethyldisilyl)aminosilane [(CHCHCHCHN)SiH{N(SiMe)}] as a colorless liquid compound represented by Formula 1-1, which was used in the film-forming composition.

[0141] 40°C at bp0.3 Torr (223.4°C at 760 Torr) 1 H-NMR(C6D6):δ0.268(N-Si-CH3,s,18H),δ1.509(N-CH2-CH * 2,m,4H), δ2.956(N-CH * 2-CH 2, m, 4H), δ 4.983 (Si-H2, s, 2H)

[0142] <Example 2> Preparation of silicon-containing film-forming compositions containing piperidinyl-(hexamethyldisilyl)aminosilane and piperidinyl-(hexamethyldisilyl)aminosilane [(CH2CH2CH2CH2CH2N)SiH2{N(SiMe3)2}] [ka]

[0143] Approximately 53.07 g (yield: approximately 95%) of piperidinyl-(hexamethyldisilyl)aminosilane [(CHCHCHCHCHN)SiH{N(SiMe)}] was obtained as a colorless liquid compound represented by formula 1-2 in the same manner as in Example 1, except that piperidine was used instead of pyrrolidine in the film-forming composition.

[0144] 87°C at bp5.5 Torr (227.8°C at 760 Torr) 1 H-NMR(C6D6):δ0.268(N-Si-CH3,s,18H),δ1.338(N-CH2-CH * 2-CH2,m,4H),δ1.432-1.445(N-CH2-CH2-CH * 2, m,2H),δ2.848(N-CH * 2-CH2-CH 2, t,4H),δ4.860(Si-H2,s,2H)

[0145] Example 3 Preparation of a silicon-containing film-forming composition containing dimethylamino-(hexamethyldisilyl)aminosilane and dimethylamino-(hexamethyldisilyl)aminosilane [{(CH3)2N}SiH2{N(SiMe3)2}] [ka]

[0146] Approximately 40.0 g (yield: approximately 85%) of dimethylamino-(hexamethyldisilyl)aminosilane [{(CH3)2N}SiH2{N(SiMe3)2}] was obtained as a colorless liquid compound represented by formula 1-8 in the same manner as in Example 1, except that dimethylamine was used in place of pyrrolidine in the film-forming composition.

[0147] 69°C at bp13 Torr (186.5°C at 760 Torr) 1 H-NMR(C6D6):δ0.242(N-Si-CH3,s,18H),δ2.407(N-CH3,s,6H),δ4.837(Si-H 2, s,2H)

[0148] Example 4 Preparation of a silicon-containing film-forming composition containing ethylmethylamino-(hexamethyldisilyl)aminosilane and ethylmethylamino-(hexamethyldisilyl)aminosilane [{(CH3CH2)(CH3)N}SiH2{N(SiMe3)2}] [ka]

[0149] Approximately 175.12 g (yield: approximately 79.6%) of ethylmethylamino-(hexamethyldisilyl)aminosilane [{(CHCH)(CH)N}SiH{N(SiMe)}] was obtained as a colorless liquid compound represented by formula 1-9 in the same manner as in Example 1, except that ethylmethylamine was used in place of pyrrolidine in the film-forming composition.

[0150] 68°C at bp9 Torr (192.1°C at 760 Torr) 1 H-NMR(C6D6):δ0.255(N-Si-CH3,s,18H),δ0.973(N-CH2-CH * 3,t,3H),δ2.417(N-CH3,s,3H),δ2.767-2.785(N-CH * 2-CH3,q,2H), δ4.873(Si-H 2, s,2H)

[0151] <Example 5> Preparation of silicon-containing film-forming compositions containing diethylamino-(hexamethyldisilyl)aminosilane and diethylamino-(hexamethyldisilyl)aminosilane [{(CH3CH2)2N}SiH2{N(SiMe3)2}] [ka]

[0152] Approximately 41.6 g (yield: approximately 79.5%) of diethylamino-(hexamethyldisilyl)aminosilane [{(CHCH)N}SiH{N(SiMe)}] was obtained as a colorless liquid compound represented by formula 1-10 in the same manner as in Example 1, except that diethylamine was used in place of pyrrolidine in the film-forming composition.

[0153] 75°C at bp6 Torr (210°C at 760 Torr) 1 H-NMR(C6D6):δ0.266(N-Si-CH3,s,18H),δ0.979(N-CH2-CH * 3,t,6H), δ2.837-2.854(N-CH * 2-CH 3, q,4H),δ4.891(Si-H 2, s,2H)

[0154] <Comparative Example 1> Tris(dimethylamino)silane (3DMAS or TDMAS) [SiH(NMe2)3] (manufactured by UP Chemical Co., Ltd.) was used.

[0155] <Comparative Example 2> Preparation of a silicon-containing film-forming composition containing pyrrolidinyl-(tetramethyldisilyl)aminosilane and pyrrolidinyl-(tetramethyldisilyl)aminosilane [(CH2CH2CH2CH2N)SiH2{N(SiHMe2)2}] [ka]

[0156] Approximately 38 g (yield: approximately 65%) of pyrrolidinyl-(tetramethyldisilyl)aminosilane [(CHCHCHCHN)SiH{N(SiHMe)}] was obtained as a colorless liquid compound represented by formula 1-11 in the same manner as in Example 1, except that tetramethyldisilazane (1,1,3,3-tetramethyldisilazane) was used in place of hexamethyldisilazane (1,1,1,3,3,3-hexamethyldisilazane) in the film-forming composition.

[0157] 32°C at bp0.3 Torr (210.3°C at 760 Torr) 1 H-NMR(C6D6):δ0.265,0.273(N-Si-CH3,d,12H),δ1.502(N-CH2-CH * 2,m,4H), δ2.973(N-CH 2, m, 4H), δ 4.827 (N-Si-H , m, 2H), δ 4.981 (Si-H2, s, 2H)

[0158] [Test example] <Test Example 1> Analysis of deposition characteristics of silicon-containing film-forming compositions containing silicon precursor compounds at high temperatures Silicon-containing films were formed by ALD using silicon-containing film-forming compositions containing the silicon precursor compounds of Examples 1 and 3 and Comparative Examples 1 and 2, respectively, and ozone (O3) as a reactive gas.

[0159] First, a silicon substrate was immersed in a piranha solution (a 4:1 mixture of sulfuric acid (H2SO4) and hydrogen peroxide (H2O2)) for approximately 10 minutes, then removed. The silicon substrate was then immersed in a dilute HF solution for 2 minutes to form a new surface. ALD was then used to form a silicon-containing oxide film on the silicon substrate.

[0160] The silicon-containing film-forming compositions containing the silicon precursor compounds of Examples 1 and 3 and Comparative Examples 1 and 2 were contained in stainless steel canisters and used at room temperature or after heating. Comparative Example 1 was used at room temperature without heating. Examples 1 and 3 and Comparative Example 2 were used after heating to 60°C. Argon (Ar) gas was flowed as a transport gas into the reactor at a flow rate of about 200 sccm and a process pressure of about 4 Torr, thereby supplying the film-forming compositions in a gaseous state to the reaction chamber.

[0161] To confirm the deposition characteristics of each silicon-containing oxide film, the following gas supply cycle was repeated 100 times to form a silicon-containing oxide film: supply the gaseous film-forming composition for approximately 3 seconds; supply argon (Ar) gas for approximately 10 seconds to remove the film-forming composition (gas) remaining in the reactor; supply ozone (O3) as a reactive gas for approximately 5 seconds; and supply argon (Ar) gas for approximately 10 seconds to remove the ozone (O3) remaining in the reactor.

[0162] The thickness of each oxide film formed using the silicon-containing film-forming compositions prepared by the methods of the Examples and Comparative Examples was measured using an ellipsometer (M-2000, JA Woollam).

[0163] The measured thickness was then divided by the number of gas supply cycles (100) to calculate the deposition rate per ALD gas supply cycle (GPC).

[0164] Specifically, the deposition rate (GPC) per cycle of ALD gas supply was measured at temperatures (process temperatures) of 600° C. to 850° C. The results are shown in FIG.

[0165] [Table 1]

[0166] As can be seen from Table 1 and FIG. 1, when ALD was performed at a high temperature of 600°C or higher using the silicon-containing film-forming compositions containing the silicon compounds of Examples 1 and 3, a consistent GPC was achieved at a relatively high temperature of 600°C to 850°C, compared to when the silicon-containing film-forming compositions containing the silicon compounds of Comparative Examples 1 and 2 were used.

[0167] Specifically, when the silicon-containing film-forming composition containing the silicon precursor compound of Comparative Example 1 was used, the film formation rate per cycle of ALD gas supply (GPC) increased from approximately 700°C. When the silicon-containing film-forming composition containing the silicon precursor compound of Comparative Example 2 was used, the film formation rate per cycle of ALD gas supply (GPC) increased from approximately 650°C. In contrast, when the silicon-containing film-forming compositions containing the silicon precursor compounds of Examples 1 and 3 were used, the film formation rate per cycle of ALD gas supply (GPC) remained constant even at high temperatures of 800°C or 850°C. From the above, it was confirmed that the silicon-containing film-forming compositions containing the silicon precursor compounds of the examples of the present invention achieved constant GPC at high temperatures of 600°C to 800°C or 850°C and exhibited self-limiting film growth characteristics. Therefore, this compound is a suitable precursor for ALD processes at high temperatures.

[0168] <Test Example 2> Analysis of the physical properties of silicon-containing oxide films deposited at high temperatures While adjusting the ALD gas supply cycle, SiO films having the same thickness were formed on flat wafers at 750° C. using the silicon-containing film-forming compositions containing the silicon precursor compounds of Examples 1 and 3 and Comparative Example 1. The physical and chemical properties of the films were analyzed.

[0169] Specifically, the shrinkage rate and wet etching rate (WER, Å / s) of the SiO2 film were measured. The thickness of the SiO2 film was measured using an ellipsometer (M-2000, JA Woollam).

[0170] By adjusting the ALD gas supply cycle, the thickness of a silicon-containing film (SiO2 film) having an initial thickness of about 100 Å formed on a flat wafer at 750°C was compared with the thickness of the silicon-containing film (SiO2 film) when annealed in an argon (Ar) atmosphere at 750°C for 60 minutes, as shown in Table 2 below, and the shrinkage rate was calculated using Equation 1. Shrinkage rate (S 750 ,%)=(AB) / A×100 [Equation 1]

[0171] In Equation 1, A is the initial thickness (Å) of the silicon-containing film formed by ALD at 750°C, and B is the thickness (Å) of the silicon-containing film formed by ALD at 750°C after aging at 750°C for 60 minutes in an argon (Ar) atmosphere.

[0172] The results are shown in Table 2.

[0173] [Table 2]

[0174] As can be seen from Table 2 above, the shrinkage rates of the silicon-containing oxide films (SiO films) deposited using the silicon-containing film-forming compositions of Examples 1 and 3 were 3.34% and 2.36%, respectively. In contrast, the shrinkage rate of the silicon-containing oxide film deposited using the silicon-containing film-forming composition of Comparative Example 1 was 6.40%. Thus, the silicon-containing oxide films deposited using the silicon-containing film-forming compositions of Examples 1 and 3 had smaller shrinkage rates than the silicon-containing oxide film deposited using the silicon-containing film-forming composition of Comparative Example 1.

[0175] Meanwhile, by adjusting the ALD gas supply cycle, a silicon-containing film (SiO film) with an initial thickness of about 500 Å formed on a flat wafer at 750°C was etched in a 1% dilute HF solution for 30 seconds, as shown in Table 3 below. The thickness change was measured to calculate the wet etching rate (WER, Å / s) according to Equation 2. Wet etch rate (Å / s) = change in etched thickness (ΔE, Å) / 30 s [Equation 2]

[0176] The change in etch thickness (ΔE) can be expressed by the following equation 2-1: Change in etching thickness (ΔE, Å) = E A -E B [Equation 2-1]

[0177] In equation 2-1, E Ais the initial thickness (Å) of the silicon-containing film formed by ALD at 750 °C, and E B is the thickness (Å) of the silicon-containing film formed by ALD at 750° C. after etching in a 1% dilute HF solution for 30 seconds.

[0178] In Equation 2, "s" means seconds.

[0179] The results are shown in Table 3 below.

[0180] [Table 3]

[0181] As can be seen from Table 3 above, the wet etching rate of the silicon-containing oxide film (SiO film) deposited using the silicon-containing film-forming composition of Example 3 was 2.51 Å / s. In contrast, the wet etching rate of the silicon-containing oxide film deposited using the silicon-containing film-forming composition of Comparative Example 1 was 2.90 Å / s. The wet etching rate of the silicon-containing oxide film deposited using the silicon-containing film-forming composition of Example 3 was significantly reduced.

[0182] On the other hand, in order to confirm impurities in the silicon-containing oxide film, secondary ion mass spectrometry (SIMS) was performed on the silicon-containing oxide film.

[0183] FIG. 2 is a graph showing the results of secondary ion mass spectrometry (SIMS) of silicon-containing oxide films deposited at a temperature of 750° C. using the silicon-containing film-forming compositions of Example 3 and Comparative Example 1 of the present invention.

[0184] In order to identify impurities in the silicon-containing oxide films deposited using the silicon-containing film-forming compositions of Comparative Example 1 and Example 3, the silicon-containing oxide films deposited to a thickness of approximately 100 Å were analyzed for carbon (C) content by SIMS.

[0185] As a result, in Example 3, the carbon content was reduced by approximately 40.6% compared to Comparative Example 1, indicating that a pure silicon-containing oxide film with a carbon component count of less than 100 was formed.

[0186] 3 shows transmission electron microscope (TEM) images of silicon-containing oxide films formed on wafers having deep patterns by ALD at 750° C. using ozone (O) and the silicon-containing film-forming compositions of Examples 1 and 3 of the present invention and Comparative Example 1. Table 4 shows the thicknesses of the silicon-containing oxide films measured at the portions shown in FIG.

[0187] [Table 4]

[0188] As can be seen from Table 4, when the silicon-containing film-forming compositions of Examples 1 and 3 and Comparative Example 1 were deposited on a substrate having steps and then analyzed using TEM, the step coverage (%) of the silicon-containing oxide films deposited using the silicon-containing film-forming compositions of Examples 1 and 3 was 96.6% and 97.8%, respectively, while the step coverage of the silicon-containing oxide film deposited using the silicon-containing film-forming composition of Comparative Example 1 was 84.3%. The silicon-containing oxide films deposited using the silicon-containing film-forming compositions of Examples 1 and 3 had significantly better step coverage than the silicon-containing oxide film deposited using the silicon-containing film-forming composition of Comparative Example 1.

[0189] 4 shows transmission electron microscope (TEM) images of silicon-containing oxide films formed on wafers having deep patterns by ALD at 650° C. using the silicon-containing film-forming compositions of Example 3 and Comparative Example 1 and ozone (O3). Table 5 shows the thicknesses of the silicon-containing oxide films measured at the portions shown in FIG.

[0190] [Table 5]

[0191] As can be seen from Table 5 above, when the silicon-containing film-forming compositions of Example 3 and Comparative Example 1 were deposited on a substrate having steps and then analyzed using TEM, the step coverage of the silicon-containing oxide film deposited using the silicon-containing film-forming composition of Example 3 was 99.8%, while the step coverage of the silicon-containing oxide film deposited using the silicon-containing film-forming composition of Comparative Example 1 was 91.4%. The silicon-containing oxide film deposited using the silicon-containing film-forming composition of Example 3 had significantly better step coverage than the silicon-containing oxide film deposited using the silicon-containing film-forming composition of Comparative Example 1.

[0192] It is expected that a silicon-containing oxide film formed at a temperature of 600°C or higher using a composition containing a silicon compound of Formula 1 other than the silicon compounds of Formula 1-1 and Formula 1-8 will be superior to a silicon-containing oxide film formed using the composition of Comparative Example 1 in terms of shrinkage rate, wet etching rate, carbon content of the film, and step coverage.

[0193] In summary, the method for forming a silicon-containing film using a silicon-containing film-forming composition including a silicon precursor compound according to an embodiment of the present invention made it possible to easily deposit a silicon-containing film by ALD, accurately control the film thickness and composition, and form a uniform film with excellent coverage even on substrates with complex shapes.

[0194] In particular, the method for forming a silicon-containing film using the silicon-containing film-forming composition containing the silicon precursor compound according to the present invention makes it possible to obtain a film of a desired thickness during deposition at high temperatures of 600° C. to 850° C. The silicon-containing oxide film thus obtained had significantly improved physical properties, such as step coverage, shrinkage rate, and wet etching rate, compared to the silicon-containing oxide film obtained using the silicon-containing film-forming composition containing the silicon precursor compound of Comparative Example 1.

Claims

1. 1. A method for forming a silicon-containing film, comprising depositing a silicon-containing film using a silicon-containing film-forming composition comprising a silicon precursor compound represented by Formula 1: 【Chemistry 1】 [In formula 1, R １ and R ２ are each independently hydrogen and linear or branched C １ ~C ４ alkyl groups, or R １ and R ２ are directly or indirectly bonded to each other and form a substituted or unsubstituted C ４ ~C ９ Forms a cyclic group, provided that C ４ ~C ９ A cyclic group contains 1 or 2 nitrogen (N) atoms and 0 to 2 oxygen (O) atoms.

2. 2. The method for forming a silicon-containing film of claim 1, wherein the silicon precursor compound comprises at least one selected from the group consisting of compounds represented by the following formula: 【Chemistry 2】

3. 10. The method of forming a silicon-containing film of claim 1, wherein the silicon-containing film is formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD) at a temperature of 600°C to 850°C.

4. SiO ２ 2. The method for forming a silicon-containing film according to claim 1, wherein when the film is formed by an atomic layer deposition (ALD) method using the silicon-containing film-forming composition, the film formation rate per cycle of ALD gas supply is 1.5 to 4.5 Å / cycle in a temperature range of 600°C to 850°C.

5. 10. The method for forming a silicon-containing film according to claim 1, comprising: delivering the silicon precursor compound to a reaction chamber using at least one method selected from the group consisting of a bubbling method, a liquid delivery system (LDS) method, a vapor flow control (VFC) method, and a bypass method.

6. 6. The method for forming a silicon-containing film of claim 5, wherein the step of supplying the silicon precursor compound to a reaction chamber is performed using a transport or dilution gas at a temperature range of room temperature to 150° C. and a pressure of 0.1 to 10 Torr.

7. 10. The method for forming a silicon-containing film of claim 1, wherein thermal energy or plasma is used or a bias is applied to the substrate during said deposition.

8. the silicon-containing film comprises at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film; Water vapor (H ２ O), oxygen (O ２ ), oxygen plasma (O ２ plasma), hydrogen peroxide (H ２ O ２ ), and ozone (O ３ ) at least one selected from the group consisting of: The method of forming the silicon-containing film of claim 1 .

9. 2. The method for forming a silicon-containing film according to claim 1, wherein the silicon-containing film is formed to a thickness ranging from 1 nm to 500 nm.

10. 10. The method for forming a silicon-containing film according to claim 1, wherein the silicon-containing film is formed on a substrate having at least one irregularity having an aspect ratio of 1 or greater and a width of 1 μm or less.

11. A silicon-containing film-forming composition comprising a silicon precursor compound represented by the following formula 1, which is used for depositing a silicon-containing film. 【Transformation 3】 [In formula 1, R １ and R ２ are each independently hydrogen and linear or branched C １ ~C ４ alkyl groups, or R １ and R ２ are directly or indirectly bonded to each other and form a substituted or unsubstituted C ４ ~C ９ Forms a cyclic group, provided that C ４ ~C ９ A cyclic group contains 1 or 2 nitrogen (N) atoms and 0 to 2 oxygen (O) atoms.

12. 12. The silicon-containing film-forming composition according to claim 11, wherein the silicon precursor compound comprises at least one selected from the group consisting of compounds represented by the following formulas: 【Chemistry 4】

13. A silicon precursor compound represented by the following formula 0: 【Transformation 5】

14. A silicon precursor compound represented by the following formula 1: 【Transformation 6】 [In formula 1, R １ and R ２ are each independently hydrogen and linear or branched C １ ~C ４ alkyl groups, or R １ and R ２ are directly or indirectly bonded to each other and form a substituted or unsubstituted C ４ ~C ９ Forms a cyclic group, provided that C ４ ~C ９ A cyclic group contains 1 or 2 nitrogen (N) atoms and 0 to 2 oxygen (O) atoms.

15. 15. The silicon precursor compound of claim 14, comprising at least one selected from the group consisting of compounds represented by the following formula: 【Transformation 7】

16. 1. Use of a silicon precursor compound represented by Formula 1 below to form a silicon-containing film. 【Transformation 8】 [In formula 1, R １ and R ２ are each independently hydrogen and linear or branched C １ ~C ４ alkyl groups, or R １ and R ２ are directly or indirectly bonded to each other and form a substituted or unsubstituted C ４ ~C ９ Forms a cyclic group, provided that C ４ ~C ９ A cyclic group contains 1 or 2 nitrogen (N) atoms and 0 to 2 oxygen (O) atoms.

17. 17. The use according to claim 16, wherein the silicon precursor compound comprises at least one selected from the group consisting of compounds represented by the following formula: 【Chemistry 9】

18. 17. The use according to claim 16, wherein the silicon-containing film is formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD) at a temperature of 600°C to 850°C.

19. SiO ２ 17. The use according to claim 16, wherein when a film is formed by an atomic layer deposition (ALD) method using the silicon precursor compound, the film formation rate per cycle of ALD gas supply is 1.5 to 4.5 Å / cycle in a temperature range of 600°C to 850°C.

20. 17. The use of claim 16, wherein the silicon-containing film is formed by a method comprising: supplying the silicon precursor compound to a reaction chamber using at least one method selected from the group consisting of a bubbling method, a liquid delivery system (LDS) method, a vapor flow control (VFC) method, and a bypass method.

21. 21. The use according to claim 20, wherein the step of supplying the silicon precursor compound to a reaction chamber is carried out using a transport gas or a dilution gas at a temperature range of room temperature to 150° C. and at a pressure of 0.1 to 10 Torr.

22. 17. The use according to claim 16, wherein the silicon precursor compound is used for depositing a silicon-containing film, and during the deposition, thermal energy or plasma is used or a bias is applied to the substrate.

23. the silicon-containing film comprises at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film; The silicon precursor compound is used to deposit a silicon-containing film, and water vapor (H ２ O), oxygen (O ２ ), oxygen plasma (O ２ plasma), hydrogen peroxide (H ２ O ２ ), and ozone (O ３ ) at least one selected from the group consisting of:

17. The use according to claim 16.

24. The use according to claim 16, wherein the silicon-containing film is formed in a thickness range of 1 nm to 500 nm.

25. 17. The use according to claim 16, wherein the silicon-containing film is formed on a substrate having at least one irregularity with an aspect ratio of 1 or more and a width of 1 μm or less.

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