Method for forming silicon-containing film, and composition therefor

Abstract

This composition for forming a silicon-containing film, comprising a silicon precursor compound represented by chemical formula 1, can efficiently form, at a high temperature of 600 °C or higher, a silicon-containing film including a silicon-containing oxide film or a silicon-containing composite metal oxide film, can control the film to have a desired thickness and composition and can form, even on a substrate with a complex shape, a silicon-containing film having excellent coverage and uniformity.

Description

Method for forming a silicon-containing film and composition therefor

[0001] The present invention relates to a method for forming a silicon-containing film and a composition therefor, and more particularly, to a method for forming a silicon-containing film at a high temperature of 600°C or higher using a composition for forming a silicon-containing film including a silicon precursor compound having a specific structure.

[0002] Silicon-containing films are one of the thin films that are essential for operating not only memory semiconductors such as DRAM, flash memory, resistive memory (ReRAM), or phase-change memory (PCRAM), but also non-memory semiconductor devices such as logic devices.

[0003] As such silicon-containing films, silicon-containing oxide films have a fast deposition rate, while silicon-containing nitride films have a slow deposition rate. For various applications, a silicon-containing film that can be selectively deposited only at a desired location is required.

[0004] In addition, as the development of products with complex shapes such as high aspect ratios and three-dimensional structures in the semiconductor and non-semiconductor fields diversifies, there is a demand for a composition for forming a silicon-containing film that includes a silicon precursor compound usable in atomic layer deposition (ALD) that is suitable for process temperatures for various applications and can overcome high step ratios.

[0005] In particular, it is important to exhibit self-limiting film growth characteristics in order to overcome the step ratio that may occur due to high integration and scale down of devices.

[0006] Accordingly, there is a need for the development of a film-forming composition including a silicon precursor compound that is suitable for ALD, forms a uniform and dense film, exhibits stress-resistant properties, and has self-limiting film growth properties even at high temperatures of 600°C or higher, and for various developments regarding a method for forming a silicon-containing film using the same.

[0007] [Prior Art Literature]

[0008] (Patent Document 1) Republic of Korea Registered Patent No. 10-0734393

[0009] The technical problem to be solved by the present invention is to provide a silicon precursor compound having a specific structure, a method for producing the compound, a composition for forming a silicon-containing film including the compound, a method for forming a silicon-containing film at a high temperature of 600°C or higher using the composition, and a silicon-containing film formed thereby.

[0010] However, the problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

[0011] The present invention provides a method for forming a silicon-containing film, comprising the step of depositing a composition for forming a silicon-containing film, which comprises a silicon precursor compound represented by the following chemical formula 1:

[0012] [Chemical Formula 1]

[0013]

[0014] In the above chemical formula 1,

[0015] R1 to R6 are each independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, except when all of R1 to R6 are hydrogen,

[0016] X is a halogen,

[0017] R7 and R8 are each independently selected from the group consisting of a linear or branched C1-C4 alkyl group and a halogen.

[0018] In addition, the present invention provides a composition for forming a silicon-containing film, which comprises a silicon precursor compound represented by the above chemical formula 1 and is used for depositing a silicon-containing film.

[0019] In addition, the present invention provides a composition for forming a silicon-containing film, which comprises a silicon precursor compound represented by the following chemical formula 1-1 and is used for depositing a silicon-containing film.

[0020] [Chemical Formula 1-1]

[0021]

[0022] In the above chemical formula 1-1,

[0023] R 11 Inland R 14 are each independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, and R 11 Inland R 14 Except when all of these are hydrogen,

[0024] X is a halogen,

[0025] R 15 and R 16 are each independently selected from the group consisting of a linear or branched C1-C4 alkyl group and a halogen.

[0026] The present invention also provides a use of a silicon precursor compound represented by the above chemical formula 1 for forming a silicon-containing film.

[0027] In addition, the present invention provides a silicon-containing film formed by the method for forming the silicon-containing film.

[0028] A method for forming a silicon-containing film according to one embodiment of the present invention can 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 composite metal oxide film at a high temperature of 600°C or higher using a silicon-containing film forming composition including a silicon precursor compound having a specific structure, and can control the thickness and composition of the film to a desired thickness and composition, and can form a silicon-containing film having excellent coverage and uniformity even on a substrate having a complex shape.

[0029] 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 penetration prevention films for organic light-emitting diode (OLED) devices, and since a film of a desired thickness can be obtained at a high temperature of 600°C or higher during film deposition, it can be very effectively utilized in electronic devices requiring excellent film properties and covering properties.

[0030]

[0031] FIG. 1 is a graph showing the deposition characteristics of a silicon-containing oxide film according to a temperature of 550°C to 850°C when depositing a silicon-containing film using a composition for forming a silicon-containing film including the silicon precursor compounds of Examples 1 and 2 of the present invention and Comparative Examples 1, 2, and 3.

[0032] FIG. 2 is a graph showing the results of secondary ion mass spectrometry (SIMS) of a silicon-containing oxide film deposited at 750°C using a composition for forming a silicon-containing film including the silicon precursor compound of Examples 1, 2, and Comparative Example 1 of the present invention.

[0033] FIG. 3 is a transmission electron microscope (TEM) image showing step coverage confirmed by depositing a silicon-containing film-forming composition including the silicon precursor compound of Examples 1, 2, and Comparative Example 1 of the present invention on a patterned wafer at 700°C and 750°C.

[0034]

[0035] The present invention is described in more detail below.

[0036] The advantages and features of the present invention, and methods for achieving them, will become clearer with reference to the embodiments described below. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms. These embodiments are provided solely to ensure complete disclosure of the present invention and to fully inform those skilled in the art of the scope of the invention. The present invention is defined solely by the scope of the claims.

[0037] Additionally, when it is said in this specification that a part is "on" another part, this includes not only cases where it is "directly on" the other part, but also cases where there is another part in between.

[0038] In this specification, when a part is said to "include" a certain component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

[0039] All numbers and expressions indicating the amounts of components, reaction conditions, etc. described in this specification should be understood to be modified by the term “about” in all cases unless otherwise specified.

[0040] In this specification, the terms “film” or “thin film” each mean both “film” and “thin film” unless specifically distinguished.

[0041] As used herein, the term "alkyl" or "alkyl group" includes linear or branched alkyl groups and all possible isomers thereof. For example, the alkyl or alkyl group may be a methyl group (Me), an ethyl group (Et), a normal propyl group ( n Pr), isopropyl group ( i Pr), normal butyl group ( n Bu), isobutyl group ( i Bu), tert-butyl group (tert-Bu, t Bu), sec-butyl group( sec Bu), as well as their isomers, but may not be limited thereto.

[0042]

[0043] [Method for forming a silicon-containing film]

[0044] According to one embodiment of the present invention, a method for forming a silicon-containing film is provided, comprising the step of depositing a composition for forming a silicon-containing film, which comprises a silicon precursor compound represented by the following chemical formula 1:

[0045] [Chemical Formula 1]

[0046]

[0047] In the above chemical formula 1,

[0048] R1 to R6 are each independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, except when all of R1 to R6 are hydrogen,

[0049] X is a halogen,

[0050] R7 and R8 are each independently selected from the group consisting of a linear or branched C1-C4 alkyl group and a halogen.

[0051] According to another embodiment of the present invention, a method for forming a silicon-containing film is provided, comprising the step of depositing a composition for forming a silicon-containing film, which comprises a silicon precursor compound represented by the following chemical formula 1-1:

[0052] [Chemical Formula 1-1]

[0053]

[0054] In the above chemical formula 1-1,

[0055] R 11 Inland R 14 are each independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, and R 11 Inland R 14 Except when all of these are hydrogen,

[0056] X is a halogen,

[0057] R 15 and R 16 are each independently selected from the group consisting of a linear or branched C1-C4 alkyl group and a halogen.

[0058] In addition, the present invention provides a composition for forming a silicon-containing film, which comprises a silicon precursor compound represented by the chemical formula 1 or chemical formula 1-1 and is used for depositing a silicon-containing film.

[0059] Specifically, the method for forming the silicon-containing film may include a step of depositing a silicon-containing film on a substrate by chemical vapor deposition (CVD) or atomic layer deposition (ALD) using a composition for forming a silicon-containing film including a silicon precursor compound represented by the chemical 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 composite metal oxide film. The deposition may be performed at a temperature of 600°C or higher, specifically, 600°C to 850°C.

[0060] In one specific example, the silicon-containing film can be formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD) at a temperature of 600°C to 850°C.

[0061] According to one embodiment of the present invention, a silicon-containing film forming composition including a silicon precursor compound having a specific structure represented by the above chemical formula 1 can be used to 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 composite metal oxide film at a high temperature of 600°C or higher, and the film thickness and composition can be controlled to a desired thickness and composition, and a silicon-containing film having excellent covering properties and uniformity can be formed even on a substrate having a complex shape.

[0062] 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 penetration prevention films for organic light-emitting diode (OLED) devices, and has technical significance in that a film of a desired thickness can be obtained at a high temperature of 600°C or higher during film deposition.

[0063] In addition, the present invention provides a composition for forming a silicon-containing film, which comprises a silicon precursor compound represented by the chemical formula 1 or chemical formula 1-1, and is used for depositing 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 composite metal oxide film.

[0064] Specifically, in the method for depositing the silicon-containing film, the formation of the silicon-containing film may include a step of depositing the silicon-containing film on a substrate (substrate) using a composition for forming a silicon-containing film including a silicon precursor compound represented by the chemical formula 1 or chemical formula 1-1.

[0065] The above substrate may be, but is not limited to, a silicon semiconductor wafer, a compound semiconductor wafer, or a plastic substrate (PI, PET, PES). In addition, a substrate having a pattern such as holes or grooves may be used, and a porous substrate with a large surface area may be used.

[0066] In particular, a silicon-containing film having a thickness of several nanometers (nm) to several micrometers (㎛) can be uniformly formed on a substrate having a pattern (groove) on the surface, a porous substrate, or a plastic substrate at a temperature range of 600°C or higher, specifically 600°C to 850°C. The pattern may be uneven, for example, a groove pattern, and specifically, may have an aspect ratio in a vertical cross-section of 1 or more, for example, about 1 to 50 or more, and a width of 1 ㎛ or less, for example, about 1 ㎛ to 10 nm or less. For example, the silicon-containing film can be formed on a substrate including one or more unevennesses having an aspect ratio of 1 or more and a width of 1 ㎛ or less. According to the present invention, there is an excellent effect of being able to form a silicon-containing film with a uniform thickness on the entire surface of the substrate including the surface of the deepest part of the fine unevenness (groove) and the surface of the fine unevenness (groove).

[0067] The method for depositing the above silicon-containing film can utilize methods, devices, etc. known in the technical field of the present invention, and, if necessary, can be performed using one or more additional reaction gases.

[0068] The deposition method of the above silicon-containing film can be performed by CVD, such as metalorganic chemical vapor deposition (MOCVD), or ALD. The MOCVD or ALD can be performed using a deposition apparatus, deposition conditions, and reaction gases known in the art.

[0069] Specifically, after accommodating a substrate in the reaction chamber, a silicon-containing film-forming composition including the silicon precursor compound is transferred onto the substrate using a carrier gas or a diluting gas, thereby depositing a silicon-containing film at a high deposition temperature of 600°C or higher, specifically, 600°C to 850°C.

[0070] Here, the above-described deposition temperature range can be applied to memory devices, logic devices, display devices, etc., and since the process temperature is wide, it has a high applicability in various fields, and in particular, by using a composition for forming a silicon-containing film including the silicon precursor compound that is resistant to a dense film and stress at high temperatures, deposition is easy in the above-described deposition temperature range.

[0071] In addition, it is preferable to use at least one mixed gas selected from the group consisting of argon (Ar), nitrogen (N2), helium (He), and hydrogen (H2) as the carrier gas or diluting gas.

[0072] In addition, the method for forming the silicon-containing film may further include a step of supplying the silicon-containing film-forming composition including the silicon precursor compound into 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. Specifically, the method for supplying the silicon-containing film-forming composition into the reaction chamber may include at least one method selected from the group consisting of a bubbling method in which the silicon-containing film-forming composition including the silicon precursor compound is forcibly vaporized using a carrier gas or a diluting gas; a liquid delivery system (LDS) method in which the composition is supplied in a liquid state at room temperature and vaporized through a vaporizer; a vapor flow control (VFC) method in which the composition is directly supplied using the vapor pressure of the precursor; and a bypass method in which the composition is vaporized through heating.

[0073] For example, when the vapor pressure is high, a gas flow rate control method can be used, when the vapor pressure is low, a bypass method of heating the container to vaporize it can be used, or a bubbling method using argon (Ar) or nitrogen (N2) gas can be used to supply the silicon-containing film-forming composition including the silicon precursor compound into the reaction chamber.

[0074] For example, the step of supplying the composition for forming the silicon-containing film into the reaction chamber can be performed using a carrier gas or a diluting gas at a pressure of 0.1 torr to 10 torr and a temperature range of room temperature to 150°C. The room temperature can be in the range of 20°C to 25°C, and as an example, can be 25°C.

[0075] More specifically, the supply method includes a bubbling method or a bypass method, and the bubbling method is performed using a carrier gas or a dilution gas in a temperature range of 0.1 torr to 10 torr and room temperature to 150°C, and the bypass method can be performed using a vapor pressure of 0.1 torr to 1.5 torr in a temperature range of room temperature to 100°C. For example, the step of supplying the composition for forming a silicon-containing film into the reaction chamber can be performed using a carrier gas or a dilution gas in a temperature range of 0.1 torr to 10 torr and room temperature to 100°C.

[0076] In addition, in order to vaporize the composition for forming a silicon-containing film including the silicon precursor compound, it can be transported using, for example, argon (Ar) or nitrogen (N2) gas. In addition, during the deposition, thermal energy or plasma can be used, or a bias can be applied to the substrate.

[0077] Meanwhile, the silicon-containing film may include a silicon-containing oxide film or a silicon-containing composite metal oxide film. Accordingly, depending on the method for forming the silicon-containing film, 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 may be deposited. During the deposition, at least one selected from the group consisting of nitrogen (N2), nitrogen plasma (N2Plasma), ammonia (NH3), ammonia plasma (NH3Plasma), hydrazine (N2H4), dimethyl hydrazine (C2H8N2), hydrogen (H2), hydrogen plasma (H2Plasma), water vapor (H2O), oxygen (O2), oxygen plasma (O2Plasma), nitric oxide (NO, N2O), nitric oxide plasma (N2O Plasma), oxygen nitride (N2O2), hydrogen peroxide (H2O2), and ozone (O3) may be used.

[0078] At least one silicon-containing film selected from the group consisting of the silicon-containing oxide film and the silicon-containing composite metal oxide film, for example, HfSiO x , ZrSiO x , TiSiO x , HfAlO x , ZrAlSiO x , TiAlSiO x , ZrHfSiO x , ZrHfAlSiO x , may include at least one selected from the group consisting of SiC and SiCO, but is not limited thereto. In this case, x may be 1 to 3.

[0079] A composition for forming a silicon-containing film comprising a silicon precursor compound represented by the above chemical formula 1 or chemical formula 1-1 is described in more detail below.

[0080]

[0081] [Composition for forming a silicon-containing film]

[0082] According to one embodiment of the present invention, a composition for forming a silicon-containing film is provided, comprising a silicon precursor compound represented by the following chemical formula 1.

[0083] [Chemical Formula 1]

[0084]

[0085] In the above chemical formula 1,

[0086] R1 to R6 are each independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, except when all of R1 to R6 are hydrogen,

[0087] X is a halogen,

[0088] R7 and R8 are each independently selected from the group consisting of a linear or branched C1-C4 alkyl group and a halogen.

[0089] The silicon precursor compound of the above chemical formula 1 may include at least one selected from the group consisting of compounds represented by the following chemical formulas:

[0090] , , , , , and .

[0091] According to another embodiment of the present invention, the silicon precursor compound of the above chemical formula 1 may be represented by the following chemical formula 1-1. Accordingly, the present invention provides a composition for forming a silicon-containing film, comprising the silicon precursor compound represented by the following chemical formula 1-1.

[0092] [Chemical Formula 1-1]

[0093]

[0094] In the above chemical formula 1-1,

[0095] R 11 Inland R 14are each independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, and R 11 Inland R 14 Except when all of these are hydrogen,

[0096] X is a halogen,

[0097] R 15 and R 16 are each independently selected from the group consisting of a linear or branched C1-C4 alkyl group and a halogen.

[0098] The silicon precursor compound of the above chemical formula 1-1 may include at least one selected from the group consisting of compounds represented by the following chemical formulas:

[0099] , , and .

[0100] Specifically, the composition for forming the silicon-containing film includes a silicon precursor compound represented by the chemical formula 1 or chemical formula 1-1, and can be used for depositing 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 can include at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film.

[0101] A composition for forming a silicon-containing film according to one embodiment of the present invention comprises a silicon precursor compound represented by the chemical formula 1 or chemical formula 1-1, thereby forming a silicon-containing film, specifically a silicon-containing oxide film, with excellent coverage and uniformity even on a substrate having a complex shape.

[0102] In particular, in the chemical formula 1 or chemical formula 1-1, the Si has a structure in which a halide having excellent reactivity with the surface and a thermally stable alkyl group are bonded, and has a structure containing three Si atoms, so that it can be more advantageous in forming a high deposition rate and a stable silicon-containing film at a high temperature of about 600°C to 850°C.

[0103] That is, in the silicon precursor compound represented by the chemical formula 1 or chemical formula 1-1, first, in the structure, the halogen element represented by -X has excellent reactivity with surfaces such as Si, Si-OH, and Si-O, which is advantageous in forming a silicon-containing oxide film; second, since the structure contains a large number of thermally stable Si and CH3 bonds, the silicon precursor does not rapidly decompose at a high temperature of 600°C or higher and can form a stable film, so that it can be suitable for a 3D NAND flash memory process that requires a dense, excellent covering property, and a uniform silicon-containing film at a high temperature; and third, since the structure contains three Si elements and has a GPC that is significantly larger in SiO2 ALD than existing silicon precursor compounds, it can be suitable for a 3D NAND flash memory process that requires forming a thick SiO2 film at a high temperature.

[0104] In addition, the present invention provides a composition for forming a silicon-containing film, which comprises a silicon precursor compound represented by the chemical formula 1 or chemical formula 1-1 and is used for depositing a silicon-containing film.

[0105] According to one embodiment of the present invention, when the silicon-containing film-forming composition is deposited by ALD, the film growth per ALD gas supply cycle (GPC) can be achieved at 1.5 to 4.5 Å / cycle at 600°C to 850°C.

[0106] Specifically, when forming a SiO2 film by ALD using the above silicon-containing film forming composition, the film growth per ALD gas supply cycle can be 1.5 to 4.5 Å / cycle in a temperature range of 650°C to 800°C.

[0107] For example, when depositing by ALD using the composition for forming a silicon-containing film, a film growth per ALD gas supply cycle (GPC) of, for example, 1.5 to 4.0 Å / cycle, 1.7 to 4.0 Å / cycle, 2.0 to 4.0 Å / cycle, 1.5 to 3.5 Å / cycle, 1.7 to 3.5 Å / cycle, 1.5 to 3.0 Å / cycle, or 2.0 to 3.0 Å / cycle can be achieved at a temperature of 600°C to 850°C, for example, 800°C.

[0108] According to one embodiment of the present invention, when a silicon-containing film is formed using the composition for forming a silicon-containing film, it is possible to control the composition to have a desired film thickness and a desired silicon content, and excellent covering properties and a uniform film can be formed even on a substrate having a pattern (groove) on the surface, a porous substrate, a plastic substrate, or a substrate having a complex shape with a three-dimensional structure, so that a high-quality silicon-containing film can be provided.

[0109] In addition, using the composition for forming the silicon-containing film, in addition to 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, 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 can be efficiently formed on a substrate by CVD or ALD.

[0110] In particular, according to one embodiment of the present invention, when 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 is formed on a substrate by ALD using the silicon-containing film forming composition, there is a great advantage in that a film having a desired thickness can be obtained at a high temperature of 600°C or higher with a uniform thickness, and a high-quality silicon-containing film having a lower film shrinkage rate and etching rate at high temperatures and having fewer impurities and being pure can be formed.

[0111]

[0112] [Uses of Silicon Precursor Compounds]

[0113] According to one embodiment of the present invention, there is provided a use of a silicon precursor compound represented by the following chemical formula 1 for forming a silicon-containing film.

[0114] [Chemical Formula 1]

[0115]

[0116] In the above chemical formula 1,

[0117] R1 to R6 are each independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, except when all of R1 to R6 are hydrogen,

[0118] X is a halogen,

[0119] R7 and R8 are each independently selected from the group consisting of a linear or branched C1-C4 alkyl group and a halogen.

[0120] The silicon precursor compound of the above chemical formula 1 may include at least one selected from the group consisting of compounds represented by the following chemical formulas:

[0121] , , , , , and .

[0122] According to another embodiment of the present invention, the silicon precursor compound of the above chemical formula 1 may be represented by the following chemical formula 1-1. Accordingly, the present invention provides a use of the silicon precursor compound represented by the following chemical formula 1-1 for forming a silicon-containing film.

[0123] [Chemical Formula 1-1]

[0124]

[0125] In the above chemical formula 1-1,

[0126] R 11 Inland R 14 are each independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, and R 11 Inland R 14 Except when all of these are hydrogen,

[0127] X is a halogen,

[0128] R 15 and R 16 are each independently selected from the group consisting of a linear or branched C1-C4 alkyl group and a halogen.

[0129] The silicon precursor compound of the above chemical formula 1-1 may include at least one selected from the group consisting of compounds represented by the following chemical formulas:

[0130] , , and .

[0131] The silicon-containing film can be formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD) at a temperature of 600°C to 850°C.

[0132] In addition, when forming a SiO2 film by atomic layer deposition (ALD) using the above silicon precursor compound, the film growth per ALD gas supply cycle can be 1.5 to 4.5 Å / cycle in a temperature range of 650°C to 800°C.

[0133] In addition, the silicon-containing film can be formed by a method including a step of supplying a silicon-containing film forming composition including the silicon precursor compound into a reaction chamber using a method including at least one 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.

[0134] Additionally, the step of supplying the silicon precursor compound into the reaction chamber can be performed using a carrier gas or a dilution gas in a temperature range of 0.1 torr to 10 torr and room temperature to 150°C.

[0135] Additionally, the silicon precursor compound is used for deposition of a silicon-containing film, and during the deposition, thermal energy or plasma may be used, or a bias may be applied to the substrate.

[0136] In addition, the silicon-containing film includes a silicon-containing oxide film or a silicon-containing composite metal oxide film, and the silicon precursor compound is used for deposition of the silicon-containing film, and during the deposition, at least one selected from the group consisting of nitrogen (N2), nitrogen plasma (N2Plasma), ammonia (NH3), ammonia plasma (NH3Plasma), hydrazine (N2H4), dimethyl hydrazine (C2H8N2), hydrogen (H2), hydrogen plasma (H2Plasma), water vapor (H2O), oxygen (O2), oxygen plasma (O2Plasma), nitric oxide (NO, N2O), nitric oxide plasma (N2O Plasma), oxygen nitride (N2O2), hydrogen peroxide (H2O2), and ozone (O3) may be used.

[0137] Additionally, the silicon-containing film can be formed in a thickness range of 1 nm to 500 nm.

[0138] Additionally, the silicon-containing film can be formed on a substrate including one or more unevennesses having an aspect ratio of 1 or more and a width of 1 μm or less.

[0139]

[0140] [Method for producing silicon precursor compounds]

[0141] [Chemical Formula 1]

[0142]

[0143] Meanwhile, the silicon precursor compound represented by the above chemical formula 1 can be manufactured by a method represented by the following reaction formula 1.

[0144] A method for producing a silicon precursor compound (chemical formula 1) according to one embodiment of the present invention may include a halide-disilazane substitution reaction step of reacting a disilazane metal salt represented by the following chemical formula B of the following reaction formula 1 with a halide silicon precursor compound represented by the following chemical formula A to form a compound of the following chemical formula 1:

[0145] [Reaction Formula 1]

[0146]

[0147] In the above reaction formula 1,

[0148] R1 to R6 are each independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, except when all of R1 to R6 are hydrogen,

[0149] R7 and R8 are each independently selected from the group consisting of a linear or branched C1-C4 alkyl group and a halogen.

[0150] X1 and X2 are each independently a halogen element, such as Cl, Br, or I.

[0151] Meanwhile, the silicon precursor compound represented by the above chemical formula 1-1 can be manufactured by the method represented by the following reaction formula 1-1.

[0152] A method for producing a silicon precursor compound (chemical formula 1-1) according to one embodiment of the present invention may include a halide-disilazane substitution reaction step of reacting a disilazane metal salt represented by the following chemical formula D of the following reaction formula 1-1 with a halide silicon precursor compound represented by the following chemical formula C to form the following chemical formula 1-1:

[0153] [Reaction Formula 1-1]

[0154]

[0155] In the above reaction formula 1-1,

[0156] R 11 Inland R 14 are each independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, and R 11 Inland R 14 Except when all of these are hydrogen,

[0157] R 15 and R 16are each independently selected from the group consisting of a linear or branched C1-C4 alkyl group and a halogen.

[0158] X1 and X2 are each independently a halogen element, such as Cl, Br, or I.

[0159]

[0160] [silicon-containing membrane]

[0161] According to one embodiment of the present invention, a silicon-containing film is provided, formed using a composition for forming a silicon-containing film including a silicon precursor compound represented by the chemical formula 1 or chemical formula 1-1.

[0162] The silicon-containing film may have a thickness of several nanometers (nm) to several micrometers (㎛) and may be applied in various ways depending on the intended use. Specifically, the silicon-containing film may be formed in a thickness range of 1 nm to 500 nm.

[0163] The above silicon-containing film can be formed on a substrate (substrate).

[0164] The above substrate is as described above.

[0165] The above silicon-containing film may include at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film.

[0166] In addition, using a composition for forming a silicon-containing film including a silicon precursor compound represented by the above chemical formula 1 or chemical formula 1-1, at least one selected from the group consisting of the silicon-containing oxide film and the silicon-containing composite metal oxide film can be efficiently formed.

[0167] In addition, the silicon-containing film is characterized by having a low shrinkage rate of the silicon-containing film and a low etching rate (Å / s) of the silicon-containing film even at a high temperature of 600°C or higher, for example, from 600°C to 850°C, by using a composition for forming a silicon-containing film including a silicon precursor compound having excellent thermal stability.

[0168] Specifically, the silicon-containing film has a shrinkage ratio (S) of the silicon-containing film represented by the following equation 1. 750 ) may be less than 5.0%:

[0169]

[0170] In the above equation 1,

[0171] A is the initial thickness (Å) of the silicon-containing film formed by ALD at 750°C,

[0172] B is the thickness (Å) of the silicon-containing film formed by ALD at 750°C after 60 minutes in an argon (Ar) atmosphere at 750°C.

[0173] The above silicon-containing film has a shrinkage ratio (S) of the silicon-containing film represented by the above formula 1. 750 ) may 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 (S) of the silicon-containing film represented by the above formula 1 750 ) may be 4.8% to 0.5%, 3.5% to 0.5%, 3.0% to 0.5%, or 2.5% to 0.5%.

[0174] The above silicone-containing film has a shrinkage ratio (S) of the silicone-containing film within the above range. 750) can be advantageous in forming a uniform and dense silicon-containing film.

[0175] Meanwhile, when the silicon-containing film is formed by deposition at 750°C with a thickness of 500 Å, when the thickness of the silicon-containing film is measured with an ellipsometer before and after exposing the silicon-containing film to an etching solution of 1% dilute hydrofluoric acid, the etching rate (Å / s) of the silicon-containing film expressed by the following Equation 2 may be 4.0 Å / s or less:

[0176] [Formula 2] Etching rate (Å / s) = Etching thickness change (ΔE, Å) / 30 s

[0177] The above etching thickness change (ΔE) can be expressed by the following equation 2-1:

[0178] [Formula 2-1] Etching thickness change (ΔE, Å) = E A - E B

[0179] In the above equation 2-1,

[0180] E A is the initial thickness (Å) of the silicon-containing film formed by ALD at 750°C,

[0181] 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.

[0182] In the above equation 2, “s” means second.

[0183] The silicon-containing film has an etching rate (Å / s) of, 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 It may be less than, 0.05 Å / s or less, or 0.03 Å / s or less. Specifically, the silicon-containing film has an etching rate (Å / s) of 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 It can be 1.0 Å / s to 0.5 Å / s.

[0184] When the above silicon-containing film satisfies the etching rate (Å / s) of the silicon-containing film within the above range, it may be advantageous in forming a uniform and dense silicon-containing film.

[0185] In addition, the silicon-containing film may have excellent step coverage.

[0186] Specifically, as shown in Fig. 3, after depositing a silicon-containing film on a substrate having a groove pattern with steps, the film is analyzed using a transmission electron microscope (TEM), and the step coverage can be calculated as shown in Equation 3 below.

[0187] [Formula 3] Step coverage (%) = B / A x 100 (%)

[0188] In the above equation 3

[0189] A is the thickness (Å) measured from the top of the home,

[0190] B is the thickness (Å) measured from the bottom (floor) of the home.

[0191] 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 silicon-containing film may have a step coverage (%) of 80% to 99%, 85% to 99%, or 95% to 99%.

[0192] Since the step coverage (%) of the silicon-containing film satisfies the above range, it is easy to control the high step ratio and fine thickness, and thus can be effectively utilized in manufacturing various semiconductor devices such as DRAM and 3D NAND flash memory.

[0193]

[0194] The present invention is described in more detail by the following examples. The following examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention.

[0195]

[0196] <Example 1> Preparation of chloro-(tetramethyldisilyl)amino-dimethyl-silane and a composition for forming a silicon-containing film containing the same: [ClSiMe2{N(SiMe2H)2}]

[0197] [Chemical Formula 2]

[0198]

[0199] In a 5 L round bottom flask, about 431.62 g (2.5 M, about 1.550 mol) of n-butyllithium hexane solution (n-BuLi in n-hexane) was mixed with about 2,500 mL of anhydrous hexane. About 206.63 g (about 1.550 mol) of 1,1,3,3-tetramethyldisilazane was added at about -20°C, and the temperature was gradually raised to room temperature while stirring, and then stirred for 4 hours. To the formed lithium(1,1,3,3-tetramethyldisilazane) salt, about 156.81 g (about 1.550 mmol) of triethylamine and about 200.00 g (about 1.550 mol) of dichlorodimethylsilane were sequentially and slowly added at -20°C to -10°C, and the temperature was gradually raised to room temperature while stirring, and then stirred for about 16 hours. After completion of the reaction, the salt produced during the reaction was removed through a filtration process, and the solvent and volatile by-products were removed by distillation under reduced pressure to obtain 226 g (yield: about 65%) of chloro-(tetramethyldisilyl)amino-dimethyl-silane [ClSiMe2{N(SiMe2H)2}] as a colorless liquid compound represented by the above chemical formula 2, which was used in a film-forming composition.

[0200] bp: 64℃ at 15 torr (177.5℃ at 760torr)

[0201] 1 H-NMR(C6D6): δ 0.220, 0.229 (N-Si-CH3, d, 12H), δ 0.450 (Cl-Si-CH3, s, 6H), δ 4.720 (N-Si-H, m, 2H).

[0202]

[0203] <Example 2> Preparation of trichloro-(tetramethyldisilyl)amino-silane and a composition for forming a silicon-containing film containing the same: [Cl3Si{N(SiMe2H)2}]

[0204] [Chemical Formula 3]

[0205]

[0206] About 465 g (yield: about 74%) of a colorless liquid compound trichloro-(tetramethyldisilyl)amino-silane [Cl3Si{N(SiMe2H)2}] represented by the chemical formula 3 was obtained in the same manner as in Example 1, except that tetrachlorosilane was used instead of dichlorodimethylsilane, and this was used in a film-forming composition.

[0207] bp: 61℃ at 10 torr (181.0℃ at 760torr)

[0208] 1 H-NMR(C6D6): δ 0.203, 0.211 (N-Si-CH3, d, 12H), δ 4.719 (N-Si-H, m, 2H)

[0209]

[0210] <Example 3> Preparation of trichloro-(hexamethyldisilyl)amino-silane and a composition for forming a silicon-containing film containing the same: [Cl3Si{N(SiMe3)2}]

[0211] [Chemical Formula 4]

[0212]

[0213] In a 3 L round bottom flask, about 163.93 g (2.5 M, about 0.59 mol) of n-butyllithium hexane solution (n-BuLi in n-hexane) was mixed with about 1,000 mL of anhydrous hexane. About 94.99 g (about 0.59 mol) of 1,1,1,3,3,3-hexamethyldisilazane was added at about -20°C, and the mixture was slowly warmed to room temperature while stirring, and then stirred for 4 hours. About 100.00 g (about 0.59 mol) of tetrachlorosilane was slowly added to the formed lithium(1,1,1,3,3,3-hexamethyldisilazane) salt at -20℃ or lower, and the temperature was gradually raised to room temperature while stirring, and then stirred for about 24 hours. After completion of the reaction, the salt produced during the reaction was removed through a filtration process, and the solvent and volatile by-products were removed by distillation under reduced pressure to obtain 75 g (yield: about 43%) of trichloro-(hexamethyldisilyl)amino-silane [Cl3Si{N(SiMe3)2}] as a white solid compound represented by the above chemical formula 4.

[0214] 1 H-NMR (C6D6): δ 0.260 (N-Si-CH3, s, 18H).

[0215]

[0216] <Comparative Example 1>

[0217] Tris(dimethylamino)silane (3DMAS or TDMAS) [SiH(NMe2)3] (product of UP Chemical Co., Ltd.) was used.

[0218]

[0219] <Comparative Example 2> Preparation of chloro-(hexamethyldisilyl)amino-silane and a composition for forming a silicon-containing film containing the same: [ClSiH2{N(SiMe3)2}]

[0220] [Chemical Formula 5]

[0221]

[0222] About 95 g (yield: about 48%) of a colorless liquid compound chloro-(hexamethyldisilyl)amino-silane [ClH2Si{N(SiMe3)2}] represented by the chemical formula 5 was obtained in the same manner as in Example 3, except that dichlorosilane was used instead of tetrachlorosilane.

[0223] bp: 73℃ at 15.2 torr (188.2℃ at 760torr)

[0224] 1 H-NMR(C6D6): δ 0.164 (N-Si-CH3, s, 18H), δ 5.148 (Cl-Si-H, s, 2H)

[0225]

[0226] <Comparative Example 3> Preparation of chloro-(tetramethyldisilyl)amino-methylsilane and a composition for forming a silicon-containing film containing the same: [ClMeHSi{N(SiMe2H)2}]

[0227] [Chemical Formula 6]

[0228]

[0229] About 123 g (yield: about 50%) of a colorless liquid compound chloro-(tetramethyldisilyl)amino-methylsilane [ClMeHSi{N(SiMe2H)2}] represented by the chemical formula 6 was obtained in the same manner as in Example 1, except that dichloromethylsilane was used instead of dichlorodimethylsilane.

[0230] bp: 40℃ at 13.6 torr (150.6℃ at 760torr)

[0231] 1H-NMR(C6D6): δ 0.172, 0.181, 0.207, 0.216 (N-Si-CH3, dd, 12H), δ 0.419, 0.426 (Cl-Si-CH3, d, 3H), δ 4.719 (N-Si-H, m, 2H), δ 5.287, 5.293 (Cl-Si-H, m, 1H).

[0232]

[0233] [Experimental Example]

[0234] <Experimental Example 1> Analysis of high-temperature deposition characteristics of a composition for forming a silicon-containing film including a silicon precursor compound

[0235] A silicon-containing film was formed by ALD using a composition for forming a silicon-containing film including the silicon precursor compounds of Examples 1 and 2 and Comparative Examples 1, 2 and 3, and ozone (O3) as a reaction gas.

[0236] First, a silicon substrate was immersed in a Piranha solution containing sulfuric acid (H2SO4) and hydrogen peroxide (H2O2) in a 4:1 ratio for about 10 minutes, then taken out and immersed in a dilute HF aqueous solution for 2 minutes to form a pure surface. A silicon-containing oxide film was formed on the silicon substrate using ALD.

[0237] The silicon-containing film-forming compositions including the silicon precursor compounds of Examples 1 and 2 and Comparative Examples 1, 2 and 3 were placed in a stainless steel container and used at room temperature. The process pressure of the reactor was set to 4 torr, and the film-forming compositions were supplied to the reaction chamber in a gaseous state by flowing argon (Ar) carrier gas at a flow rate of about 200 sccm.

[0238] In order to confirm the deposition characteristics of each silicon-containing oxide film, a gas supply cycle consisting of supplying a film-forming composition in a gaseous state for about 3 seconds → supplying argon (Ar) gas for about 10 seconds to remove the film-forming composition (gas) remaining in the reactor → supplying ozone (O3) as a reaction gas for about 5 seconds → supplying argon (Ar) gas for about 10 seconds to remove the ozone (O3) gas remaining in the reactor was repeated 100 times to form a silicon-containing oxide film.

[0239] The thickness of each oxide film formed using the silicon-containing film-forming composition manufactured by the method of the above examples and comparative examples was measured using an ellipsometer (JA Woollam, M-2000).

[0240] Afterwards, the measured thickness was divided by the number of gas supply cycles (100 times) to measure the film growth per ALD gas supply cycle (GPC).

[0241] Specifically, film growth (GPC) per ALD gas supply cycle was measured at temperatures (process temperatures) of 550°C to 850°C, and the results are shown in Fig. 1 and Table 1.

[0242]

[0243]

[0244] As can be seen in Table 1 and Fig. 1, when ALD was performed at a high temperature of 550°C or higher using a composition for forming a silicon-containing film including the silicon precursor compounds of Examples 1 and 2, it was found that GPC was constant up to a relatively high temperature of 650°C or higher and 800°C or higher.

[0245] Specifically, when the silicon-containing film-forming composition including the silicon precursor compound of Comparative Example 1 was used, it was confirmed that the film growth (GPC) per ALD gas supply cycle increased from about 750°C, whereas when the silicon-containing film-forming composition including the silicon precursor compounds of Examples 1 and 2 was used, the film growth (GPC) per ALD gas supply cycle was constant even at a high temperature of 800°C. From this, it can be confirmed that the silicon-containing film-forming composition including the silicon precursor compound of the example of the present invention is a precursor suitable for a high-temperature ALD process because it exhibits a constant GPC and self-limiting film growth characteristics at a high temperature of 650°C to 800°C.

[0246] In addition, when using a composition for forming a silicon-containing film including the silicon precursor compound of Comparative Examples 2 and 3, it was found that the film growth rate greatly increased with temperature from 550°C and that ALD characteristics were not observed. Unlike Examples 1 and 2, Comparative Examples 2 and 3 did not exhibit ALD characteristics in the temperature range of 550 to 800°C. This is because when a hydrogen atom is bonded to a silicon atom to which a halogen is bonded, instability occurs during the film formation process, making it difficult to stably form a film.

[0247]

[0248] <Experimental Example 2> Analysis of the physical properties of high-temperature deposited silicon-containing oxide films

[0249] The physical and chemical properties of SiO2 films formed with the same thickness on a flat wafer at 650°C to 800°C by controlling the ALD gas supply cycle using a composition for forming a silicon-containing film including the silicon precursor compound of Examples 1, 2, and Comparative Example 1 were analyzed.

[0250] Specifically, the shrinkage and wet etch rate (WER, Å / s) of the SiO2 film were measured. The thickness of the SiO2 film was measured using an ellipsometer (JA Woollam, M-2000).

[0251] The thickness of a silicon-containing film (SiO2 film) formed with an initial thickness of approximately 100 Å on a flat wafer at 750°C by controlling the ALD gas supply cycle as shown in Table 2 below was compared with the thickness of a silicon-containing film (SiO2 film) after annealing at 750°C for 60 minutes in an argon (Ar) atmosphere, and the shrinkage of Equation 1 below was calculated.

[0252]

[0253] In the above equation 1,

[0254] A is the initial thickness (Å) of the silicon-containing film formed by ALD at 750°C,

[0255] B is the thickness (Å) of the silicon-containing film formed by ALD at 750°C after 60 minutes in an argon (Ar) atmosphere at 750°C.

[0256] The results are shown in Table 2.

[0257]

[0258]

[0259] As can be seen in Table 2 above, the shrinkage rates of the silicon-containing oxide films (SiO2 films) deposited using the silicon-containing film-forming compositions of Examples 1 and 2 were 3.34% and 2.97%, respectively, whereas the shrinkage rate of the silicon-containing oxide film deposited using the silicon-containing film-forming composition of Comparative Example 1 was 10.79%. Thus, the silicon-containing oxide films deposited using the silicon-containing film-forming compositions of Examples 1 and 2 had lower film shrinkage rates at high temperatures than the silicon-containing oxide films deposited using the silicon-containing film-forming composition of Comparative Example 1.

[0260]

[0261] Meanwhile, a silicon-containing film (SiO2 film) formed with an initial thickness of approximately 500 Å on a flat wafer at 750°C by controlling the ALD gas supply cycle as shown in Table 3 below was etched in a 1% dilute HF solution for 30 seconds, and the thickness change was measured to calculate the etching rate (WER, wet etch rate, Å / s) of Equation 2 below.

[0262] [Formula 2] Etching rate (Å / s) = Etching thickness change (ΔE, Å) / 30 s

[0263] The above etching thickness change (ΔE) can be expressed by the following equation 2-1:

[0264] [Formula 2-1] Etching thickness change (ΔE, Å) = E A - E B

[0265] In the above equation 2-1,

[0266] E A is the initial thickness (Å) of the silicon-containing film formed by ALD at 750°C,

[0267] 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.

[0268] In the above equation 2, “s” means second.

[0269] The results are shown in Table 3 below.

[0270]

[0271]

[0272] As can be seen in Table 3 above, the etching rates of the silicon-containing oxide films (SiO2 films) deposited using the silicon-containing film-forming compositions of Examples 1 and 2 are 2.50 Å / s and 3.81 Å / s, respectively, while the etching rate of the silicon-containing oxide film deposited using the silicon-containing film-forming composition of Comparative Example 1 is 2.74 Å / s, confirming that the etching rate (Å / s) of the silicon-containing oxide films formed using the silicon-containing film-forming compositions of Examples 1 and 2 is comparable to or superior to that of the silicon-containing oxide film deposited using the silicon-containing film-forming composition of Comparative Example 1.

[0273]

[0274] Meanwhile, in order to confirm the impurities in the silicon-containing oxide film, secondary ion mass spectrometry (SIMS) of the silicon-containing oxide film was measured.

[0275] FIG. 2 is a graph showing the results of secondary ion mass spectrometry (SIMS) of a silicon-containing oxide film deposited at 750°C using the silicon-containing film forming compositions of Examples 1 and 2 and Comparative Example 1 of the present invention.

[0276] To confirm the impurities in the silicon-containing oxide film deposited using the silicon-containing film forming composition of Examples 1, 2, and Comparative Example 1, the carbon (C) component of the silicon-containing oxide film deposited to about 120 Å was analyzed using SIMS.

[0277] As a result, it was found that the content of carbon components in both Examples 1 and 2 was reduced by approximately 95% compared to Comparative Example 1, and it was confirmed that a pure silicon-containing oxide film with a carbon component of less than 100 Counts was formed.

[0278]

[0279] FIG. 3 is a transmission electron microscope (TEM) image of a silicon-containing oxide film formed on a substrate having a deep groove pattern at 750°C by ALD using the silicon-containing film-forming compositions of Examples 1 and 2 and Comparative Example 1 of the present invention and ozone (O3). The thickness of the silicon-containing oxide film measured at the portion indicated in FIG. 3 and the step coverage (%) calculated according to Equation 3 below are shown in Table 4.

[0280] [Formula 3] Step coverage (%) = B / A x 100 (%)

[0281] In the above equation 3

[0282] A is the thickness (Å) measured from the top of the home,

[0283] B is the thickness (Å) measured from the bottom (floor) of the home.

[0284]

[0285]

[0286] As can be seen in Table 4, when the silicon-containing film-forming compositions of Examples 1, 2 and Comparative Example 1 were deposited on a stepped substrate at 700°C and 750°C, and the results of analysis using TEM showed that the step coverage (%) of the silicon-containing oxide films deposited at 750°C using the silicon-containing film-forming compositions of Examples 1 and 2 was 98.1% and 96.2%, respectively, whereas the step coverage (%) of the silicon-containing oxide films deposited at 750°C using the silicon-containing film-forming composition of Comparative Example 1 was 84.3%, indicating that the step coverage of the silicon-containing oxide films formed using the silicon-containing film-forming compositions of Examples 1 and 2 was significantly superior to the step coverage of the silicon-containing oxide films formed using the silicon-containing film-forming composition of Comparative Example 1.

[0287] It can be expected that a silicon-containing oxide film formed at a temperature of 650°C or higher using a composition including not only silicon compounds of chemical formulae 2 and 3 but also other silicon compounds represented by chemical formulae 1 and 1-1 will have superior shrinkage rate, etching rate, carbon component content of the film, and step coverage compared to a silicon-containing oxide film formed using the composition of Comparative Example 1.

[0288] In summary, according to a method for forming a silicon-containing film using a composition for forming a silicon-containing film including a silicon precursor compound according to one embodiment of the present invention, not only can a silicon-containing film be easily deposited by ALD, but the thickness and composition of the film can be precisely controlled, and a film with excellent coverage and uniformity can be formed even on a substrate of a complex shape.

[0289] In particular, according to the method for forming a silicon-containing film using the composition for forming a silicon-containing film including the silicon precursor compound of the present invention, a film having a desired thickness can be obtained at a high temperature of 650°C to 800°C during deposition, and it can be seen that the physical properties of the silicon-containing oxide film thus obtained, such as step coverage, shrinkage rate, and etching rate, are significantly improved compared to the silicon-containing oxide film using the composition for forming a silicon-containing film including the silicon precursor compound of Comparative Example 1.

Claims

1. A method for forming a silicon-containing film, comprising the step of depositing a composition for forming a silicon-containing film, which comprises a silicon precursor compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R1 to R6 are each independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, except when all of R1 to R6 are hydrogen, X is a halogen, R7 and R8 are each independently selected from the group consisting of a linear or branched C1-C4 alkyl group and a halogen.

2. In paragraph 1, A method for forming a silicon-containing film, wherein the silicon precursor compound comprises at least one selected from the group consisting of compounds represented by the following chemical formula: , , , , , and .

3. In paragraph 1, A method for forming a silicon-containing film, 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. In paragraph 3, A method for forming a silicon-containing film, wherein when forming a SiO2 film by atomic layer deposition (ALD) using the above silicon-containing film forming composition, the film growth per ALD gas supply cycle is 1.5 to 4.5 Å / cycle in a temperature range of 650°C to 800°C.

5. In paragraph 1, A method for forming a silicon-containing film, comprising the step of supplying a composition for forming a silicon-containing film including a silicon precursor compound into a reaction chamber using a method including at least one 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. In paragraph 5, A method for forming a silicon-containing film, wherein the step of supplying the composition for forming the silicon-containing film into the reaction chamber is performed using a carrier gas or a diluting gas in a pressure range of 0.1 torr to 10 torr and a temperature range of room temperature to 150°C.

7. In paragraph 1, A method for forming a silicon-containing film, wherein thermal energy or plasma is used during the above deposition, or a bias is applied to the substrate.

8. In paragraph 1, The above silicon-containing film comprises a silicon-containing oxide film or a silicon-containing composite metal oxide film, A method for forming a silicon-containing film, wherein, during the above deposition, at least one selected from the group consisting of nitrogen (N2), nitrogen plasma (N2Plasma), ammonia (NH3), ammonia plasma (NH3Plasma), hydrazine (N2H4), dimethyl hydrazine (C2H8N2), hydrogen (H2), hydrogen plasma (H2Plasma), water vapor (H2O), oxygen (O2), oxygen plasma (O2Plasma), nitric oxide (NO, N2O), nitric oxide plasma (N2O Plasma), oxygen nitride (N2O2), hydrogen peroxide (H2O2), and ozone (O3) is used.

9. In paragraph 1, A method for forming a silicon-containing film, wherein the silicon-containing film is formed in a thickness range of 1 nm to 500 nm.

10. In paragraph 1, A method for forming a silicon-containing film, wherein the silicon-containing film is formed on a substrate including one or more unevennesses having an aspect ratio of 1 or more and a width of 1 ㎛ or less.

11. A composition for forming a silicon-containing film, comprising a silicon precursor compound represented by the following chemical formula 1 and used for depositing a silicon-containing film: [Chemical Formula 1] In the above chemical formula 1, R1 to R6 are each independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, except when all of R1 to R6 are hydrogen, X is a halogen, R7 and R8 are each independently selected from the group consisting of a linear or branched C1-C4 alkyl group and a halogen.

12. In paragraph 11, A composition for forming a silicon-containing film, wherein the silicon precursor compound comprises at least one selected from the group consisting of compounds represented by the following chemical formula: , , , , , and .

13. In paragraph 11, The silicon precursor compound of the above chemical formula 1 is a composition for forming a silicon-containing film, represented by the following chemical formula 1-1: [Chemical Formula 1-1] In the above chemical formula 1-1, R 11 Inland R 14 are each independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, and R 11 Inland R 14 Except when all of these are hydrogen, X is a halogen, R 15 and R 16 are each independently selected from the group consisting of a linear or branched C1-C4 alkyl group and a halogen.

14. In paragraph 13, A composition for forming a silicon-containing film, wherein the silicon precursor compound comprises at least one selected from the group consisting of compounds represented by the following chemical formula: , , and .

15. Use of a silicon precursor compound represented by the following chemical formula 1 for forming a silicon-containing film: [Chemical Formula 1] In the above chemical formula 1, R1 to R6 are each independently selected from the group consisting of hydrogen and linear or branched C1-C4 alkyl groups, except when all of R1 to R6 are hydrogen, X is a halogen, R7 and R8 are each independently selected from the group consisting of a linear or branched C1-C4 alkyl group and a halogen.

Images