Precursor for forming low-permittivity silicon-containing thin film, and method for forming low-permittivity silicon-containing thin film by using same

Abstract

The present invention relates to: a precursor for forming a low-permittivity silicon-containing thin film, comprising a silicon-containing compound represented by chemical formula 1; and a method for forming a thin film by using the precursor, and, to a precursor for forming a silicon-containing thin film, and a method for forming a silicon-containing thin film by using same, the precursor having an excellent thin film growth rate when applied to a thin film formation process, and exhibiting physical properties enabling a high-quality silicon-containing thin film to be formed.

Description

A precursor for forming a low-k silicon-containing thin film and a method for forming a low-k silicon-containing thin film using the same.

[0001] The present invention relates to a precursor for forming a silicon-containing thin film and a method for forming a silicon-containing thin film using the same, and more particularly, to a precursor for forming a silicon-containing thin film which can form a high-quality silicon-containing thin film when applied to a thin film forming process by using a novel disilane compound as a precursor, and a method for forming a silicon-containing thin film using the same.

[0002] As semiconductor devices become smaller and more integrated, parasitic capacitance increases, which in turn causes response speed delay (RC delay). Research and development are being conducted to address this. This parasitic capacitance is primarily caused by the metal wirings becoming very close together, resulting in the arrangement of the metal wirings having a structure similar to that of a capacitor. To reduce this, it is necessary to form the interlayer insulating film formed between the metal wirings with an insulating material having a low dielectric constant.

[0003] The insulating material having the above low dielectric constant can be formed by the spin-on dielectric (SOD) method and the chemical vapor deposition (CVD) method, and examples thereof include a fluorinated silicon oxide film (Fluorinated Silicate Glass, FSG film) and a SiOC film.

[0004] Conventionally, precursors used to form low-k thin films include octamethylcyclotetrasiloxane (OMCTS), diethoxymethylsilane (DEMS), and tetraethoxyorthosilicate (TEOS). These precursors are in a liquid state, which is advantageous for vaporization for the deposition process, but their application to the thin film formation process is limited, such as difficulty in obtaining a sufficient elastic modulus in the formed thin film.

[0005] For example, in the Republic of Korea Patent Publication No. 10-2006-0029762, MTES, DEMS, DMOMS, TOMCATS, DMDMOS, DMDOSH, Z3MS, etc. are used as organosiloxane source gases in a process of forming an insulating film using SiH4 and SiF4 gases. However, the organosiloxane source is additionally added to the precursor, so there is a limit to lowering the dielectric constant. In addition, when the organosiloxane source is used as a precursor, there is a problem that the elastic modulus is lowered, which limits its use in the thin film formation process.

[0006] In addition, Korean Patent Publication No. 10-1215033 discloses a technology for forming a high-quality silicon-containing thin film using silicon precursors such as silane, dimethylsilane, trimethylsilane, tetramethylsilane, diethylsilane, tetramethylorthosilicate (TMOS), tetraethylorthosilicate (TEOS), octamethyltrisiloxane (OMTS), octamethylcyclotetrasiloxane (OMCTS), tetramethyldimethyldimethoxydisilane, tetramethylcyclotetrasiloxane (TOMCATS), dimethyl dimethoxysilane (DMDMOS), diethoxymethylsilane (DEMS), methyltriethoxysilane (MTES), phenyldimethylsilane, and phenylsilane. However, this thin film forming method has a limitation in that it cannot sufficiently increase the growth speed of the silicon oxide layer because it uses a conventional silicon precursor.

[0007] The present invention has been devised in consideration of the above-described prior arts, and its purpose is to provide a precursor which is a compound containing disilane and which is liquid at room temperature and thus easy to store and handle, has an excellent thin film growth rate due to the high reactivity of disilane, and can form a high-quality, low-k silicon-containing thin film.

[0008] In addition, the purpose is to provide a thin film forming method capable of forming a low-k silicon-containing thin film by using the precursor for forming the low-k silicon-containing thin film.

[0009] In order to achieve the above purpose, the precursor for forming a low dielectric constant silicon-containing thin film of the present invention is characterized by including a silicon-containing compound represented by the following chemical formula 1.

[0010] [Chemical Formula 1]

[0011]

[0012] In the above chemical formula 1, R1 to R4 are each independently a hydrogen atom or a C1-C6 straight-chain, branched or cyclic alkyl group, an allyl group including a C1-C6 straight-chain, branched or cyclic functional group, a vinyl group including a C1-C6 straight-chain, branched or cyclic functional group, a primary or secondary amine group, or a phenyl group including or not including a C1-C6 functional group, X is a functional group capable of bonding to a silicon atom, and Y is any one of the following structural formulas 1 to 3,

[0013] [Structural formula 1]

[0014]

[0015] [Structural formula 2]

[0016]

[0017] [Structural formula 3]

[0018]

[0019] In the above structural formula 1 or 2, R5 to R7 are each independently a hydrogen atom or a C1-C6 straight-chain, branched or cyclic alkyl group, n is an integer from 0 to 3, in the above structural formula 1, Z is any one selected from NR (wherein, R" is a hydrogen atom or a C1-C6 straight-chain or branched alkyl group or alkenyl group), O, S, and in the above structural formula 3, R8 to R 10 are each independently a hydrogen atom or a C1-C6 straight-chain, branched or cyclic alkyl group, an allyl group containing a C1-C6 straight-chain, branched or cyclic functional group, a vinyl group containing a C1-C6 straight-chain, branched or cyclic functional group, a primary or secondary amine group, or a phenyl group containing or not containing a C1-C6 functional group.

[0020] At this time, X may be the same as Y, and X may be different from Y, and X is a hydrogen atom, or a C1-C6 straight-chain or cyclic alkyl group or alkenyl group, an alkoxy group, or -OSiR 11 R 12 R 13 (Here, R 11 Inland R 13 may each independently be any one of a hydrogen atom or a C1-C6 straight-chain, branched or cyclic alkyl group, an allyl group containing a C1-C6 straight-chain, branched or cyclic functional group, a vinyl group containing a C1-C6 straight-chain, branched or cyclic functional group, a primary or secondary amine group, or a phenyl group containing or not containing a C1-C6 functional group.

[0021] Additionally, the precursor for forming the low dielectric constant silicon-containing thin film may additionally include a solvent.

[0022] The above solvent is C1-C 16One or more solvents selected from the group consisting of saturated or unsaturated hydrocarbons, ketones, ethers, glymes, esters, tetrahydrofuran, and tertiary amines may be used, and may be included in an amount of 1 to 99 wt% based on the total weight of the precursor for forming the low-k silicon-containing thin film.

[0023] The method for forming a low-k silicon-containing thin film of the present invention is characterized by including a process of forming a thin film on a substrate using the precursor for forming the low-k silicon-containing thin film.

[0024] At this time, the process of forming a thin film on the substrate may include a process of forming a precursor thin film by depositing a precursor for forming the thin film on the surface of the substrate, and a process of reacting the precursor thin film with a reactive gas.

[0025] Additionally, the reactive gas may be one or more of nitrogen (N2), ammonia (NH3), hydrazine (N2H4), nitrous oxide (N2O), oxygen (O2), water vapor (H2O), ozone (O3), hydrogen peroxide (H2O2), silane (SiH4), hydrogen (H2), and diborane (B2H6).

[0026] Additionally, the process for forming the precursor thin film may include a process for vaporizing the precursor for forming the low-k silicon-containing thin film and transporting it into the chamber.

[0027] Additionally, the deposition may be performed by any one of a Spin-On Dielectric (SOD) process, a Low Temperature Plasma (LTP) process, a Chemical Vapor Deposition (CVD) process, a Plasma Enhanced Chemical Vapor Deposition (PECVD) process, a High Density Plasma Chemical Vapor Deposition (HDPCVD) process, an Atomic Layer Deposition (ALD) process, or a Plasma Enhanced Atomic Layer Deposition (PEALD) process.

[0028] In addition, the process of forming a thin film on the substrate may include a step of supplying a precursor for forming a thin film containing low dielectric constant silicon to the substrate and applying plasma to form a thin film.

[0029] The precursor according to the present invention is a disilane compound having a chemical structure represented by chemical formula 1, which can form a high-quality silicon-containing thin film.

[0030] In addition, by using the precursor for forming the low-k silicon-containing thin film, a low-k silicon-containing thin film having a high elastic modulus can be formed, thereby providing a method for forming a thin film that can be used for purposes such as next-generation DRAM IMD (Inter Metal Dielectric).

[0031] Figure 1 is a diagram of the compound obtained in Example 1. 1 This is the result of H-NMR analysis.

[0032] Figure 2 is a diagram of the compound obtained in Example 2. 1 This is the result of H-NMR analysis.

[0033] Figure 3 is a diagram of the compound obtained in Example 3. 1This is the result of H-NMR analysis.

[0034] Figure 4 is a diagram of the compound obtained in Example 4. 1 This is the result of H-NMR analysis.

[0035] Figure 5 is a diagram of the compound obtained in Example 5. 1 This is the result of H-NMR analysis.

[0036] Figure 6 is a diagram of the compound obtained in Example 6. 1 This is the result of H-NMR analysis.

[0037] Figure 7 is a diagram of the compound obtained in Example 7. 1 This is the result of H-NMR analysis.

[0038] Figure 8 shows the results of thermogravimetric analysis (TGA) of the compounds obtained in Examples 1 to 7.

[0039] The present invention will be described in more detail below. Terms and words used in this specification and claims should not be construed as limited to their conventional or dictionary meanings. Rather, they should be interpreted in a way that is consistent with the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of a term to best explain his or her invention.

[0040]

[0041] A precursor for forming a low-k silicon-containing thin film according to the present invention is characterized by including a silicon-containing compound represented by the following chemical formula 1.

[0042] [Chemical Formula 1]

[0043]

[0044] In the above chemical formula 1, R1 to R4 are each independently a hydrogen atom or a C1-C6 straight-chain, branched or cyclic alkyl group, an allyl group including a C1-C6 straight-chain, branched or cyclic functional group, a vinyl group including a C1-C6 straight-chain, branched or cyclic functional group, a primary or secondary amine group, or a phenyl group including or not including a C1-C6 functional group, X is a functional group capable of bonding to a silicon atom, and Y is any one of the following structural formulas 1 to 3,

[0045] [Structural formula 1]

[0046]

[0047] [Structural formula 2]

[0048]

[0049] [Structural formula 3]

[0050]

[0051] In the above structural formula 1 or 2, R5 to R7 are each independently a hydrogen atom or a C1-C6 straight-chain, branched or cyclic alkyl group, n is an integer from 0 to 3, in the above structural formula 1, Z is any one selected from NR (wherein, R" is a hydrogen atom or a C1-C6 straight-chain or branched alkyl group or alkenyl group), O, S, and in the above structural formula 3, R8 to R 10 are each independently a hydrogen atom or a C1-C6 straight-chain, branched or cyclic alkyl group, an allyl group containing a C1-C6 straight-chain, branched or cyclic functional group, a vinyl group containing a C1-C6 straight-chain, branched or cyclic functional group, a primary or secondary amine group, or a phenyl group containing or not containing a C1-C6 functional group.

[0052] The above X may be the same as or different from Y. When X and Y are different, the above X is a hydrogen atom, or a C1-C6 straight-chain or cyclic alkyl or alkenyl group, an alkoxy group, or -OSiR 11 R 12 R 13 (Here, R 11 Inland R 13 may each independently be any one of a hydrogen atom or a C1-C6 straight-chain, branched or cyclic alkyl group, an allyl group containing a C1-C6 straight-chain, branched or cyclic functional group, a vinyl group containing a C1-C6 straight-chain, branched or cyclic functional group, a primary or secondary amine group, or a phenyl group containing or not containing a C1-C6 functional group.

[0053] In addition, the precursor of the present invention may additionally include a solvent. The solvent may be C1-C 16 Any one or a mixture of saturated or unsaturated hydrocarbons, ketones, ethers, glymes, esters, tetrahydrofuran, and tertiary amines may be used. The C1-C 16 Examples of saturated or unsaturated hydrocarbons include toluene and heptane, and examples of tertiary amines include dimethylethylamine.

[0054] In particular, when the silicon-containing compound forms a solid state at room temperature or a temperature slightly higher than that, it is preferable to include a solvent capable of dissolving it. That is, when the solvent is included, it is included in a solvent and content capable of dissolving the silicon-containing compound, and it is preferable to include it in an amount of 1 to 99 wt% based on the total weight of the precursor for forming the silicon-containing thin film.

[0055] Since the precursor, with or without the solvent, is vaporizable, it can be supplied into the chamber in the form of a precursor gas. Accordingly, depending on the type of silicon-containing compound, if it exists in a liquid state at room temperature and can be easily vaporized, the thin film formation process can be performed without a separate solvent.

[0056] That is, the method for forming a low-k silicon-containing thin film of the present invention may include a process of forming a thin film on a substrate using a precursor for forming a low-k silicon-containing thin film.

[0057] Specifically, the process for forming a thin film on a substrate may include a process for forming a precursor thin film by depositing a precursor for forming the thin film on the surface of the substrate, and a process for reacting the precursor thin film with a reactive gas. At this time, the reactive gas may be one or more of nitrogen (N2), ammonia (NH3), hydrazine (N2H4), nitrous oxide (N2O), oxygen (O2), water vapor (H2O), ozone (O3), hydrogen peroxide (H2O2), silane (SiH4), hydrogen (H2), and diborane (B2H6).

[0058] In addition, the step of vaporizing the precursor for forming the low-k silicon-containing thin film and transporting it into the chamber may be included, and the thin film may be formed by supplying the precursor for forming the low-k silicon-containing thin film onto a substrate and then applying plasma to deposit the precursor.

[0059] Specifically, the deposition process may be performed by any one of a Spin-On Dielectric (SOD) process, a Low Temperature Plasma (LTP) process, a Chemical Vapor Deposition (CVD) process, a Plasma Enhanced Chemical Vapor Deposition (PECVD) process, a High Density Plasma Chemical Vapor Deposition (HDPCVD) process, an Atomic Layer Deposition (ALD) process, or a Plasma Enhanced Atomic Layer Deposition (PEALD) process.

[0060] For example, when the HDPCVD process is applied, it can be performed under high vacuum and high power compared to the atmospheric pressure chemical vapor deposition process (APCVD), low pressure chemical vapor deposition process (LPCVD), or plasma enhanced chemical vapor deposition process (PECVD), so it is possible to form a thin film that is structurally dense and has excellent mechanical properties.

[0061] In addition, when applying plasma, the plasma may be applied while a source gas other than the precursor for forming the low-k silicon-containing thin film transferred into the chamber is supplied to the substrate.

[0062] For example, by supplying a precursor gas for forming a low-k silicon-containing thin film, oxygen gas, and hydrogen gas as a carrier gas onto a substrate on which a metal wiring pattern is formed, and generating plasma therein, a low-k interlayer insulating film that fills the gap between the metal wiring patterns formed on the substrate can be formed. In addition, when it is desired to form a silicon fluoride insulating film, a fluorine source gas can be supplied together to form the thin film.

[0063] In addition, depending on the type of interlayer insulating film, a low dielectric constant insulating film that fills the gap between metal wiring patterns on the substrate can be formed by supplying an inert gas such as argon (Ar) or helium (He) gas together with a silicon source gas, a fluorine source gas, an oxygen gas, and a gas containing carbon on the substrate and generating plasma.

[0064] As the above fluorine source, SiF4, which is commonly used, can be used, and as a gas containing carbon, a hydrocarbon gas such as CH4, C2H4, C2H6, C2H2, C6H6, or an organosiloxane source gas such as methylethoxysilane (MTES), diethoxymethylsilane (DEMS), dimethoxymethylsilane (DMOMS), tetramethylcyclotetrasiloxane (TOMCATS), dimethyldimethoxysilane (DMDMOS), dimethyldeoxysilylcyclohexane (DMDOSH), or trimethylsilane (TMS) can be used.

[0065] The process for forming the above thin film can be performed under chamber pressure conditions of 0.1 to 10 Torr. In addition, the source power for forming plasma within the chamber is appropriately 50 to 9,000 W, and the bias power is appropriately 0 to 5,000 W. In addition, the bias power may not be applied in some cases.

[0066] In the above-described thin film formation process, the structural characteristics of the silicon-containing compound used in the present invention cause the formation of microscopic pores when forming the interlayer insulating film. By forming these pores, the dielectric constant of the interlayer insulating film can be further reduced, and a lower dielectric constant can be achieved compared to existing interlayer insulating films.

[0067] In addition, the mechanical properties of the formed thin film are improved because the bonding strength between the silicon-containing compound and the thin film surface is improved.

[0068] In addition, by applying the above thin film formation process, a semiconductor device characterized by including a low-k silicon-containing thin film can be manufactured. At this time, the low-k silicon-containing thin film forms an FSG (Fluorinated Silicate Glass) film or an OSG (Organo Silicate Glass) film as an interlayer insulating film, thereby reducing parasitic capacitance between wirings of the semiconductor device, thereby forming a high-quality semiconductor device.

[0069] Thus, the thin film obtained by applying the thin film formation method of the present invention exhibits excellent physical properties. Therefore, a low-k dielectric thin film with a high elastic modulus can be obtained through these thin film properties, and thus can be used in semiconductor devices such as next-generation DRAM IMD.

[0070] The effects of the present invention are explained through the following examples.

[0071] Manufacturing Example 1. Manufacturing of N,N-diisopropyl-1,1,2,2-tetramethyl-2-(prop-1-en-2-yloxy)disilan-1-amine

[0072] 100 ml of dichloromethane was cooled to a low temperature (approximately 0°C), 20 g (0.107 mol) of 1,2-dichlorotetramethyldisilane was added, and 21.6 g (30.2 ml, 0.428 mol) of diisopropylamine was slowly added at a low temperature (approximately -5 to 0°C) over 1 hour, and stirred at room temperature for approximately 18 hours. The reactant was filtered, and the solvent of the obtained filtrate was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [74℃@3.9torr] to obtain 24.5 g (yield: 60%) of 2-chloro-N,N-diisopropyl-1,1,2,2-tetramethyldisilan-1-amine as a colorless liquid.

[0073] The characteristic peaks of the NMR analysis results of the product are as follows.

[0074] 1 H-NMR(C6D6): δ 0.33 [s, 6H, -Si(CH3)2-Cl], 0.44 [s, 6H, -Si(CH3)2-N-], 0.98-1.00 [d, 12H, -SiN(CH(CH3)2)2], 3.06 [m, 2H, -SiN(CH(CH3)2)2]

[0075] 120 ml of acetonitrile was cooled to a low temperature (approximately -10°C), and 14.5 g (0.097 mol) of sodium iodide was added. 24.4 g of the synthesized 2-chloro-N,N-diisopropyl-1,1,2,2-tetramethyldisilan-1-amine was added, stirred at room temperature for 1 hour, and then re-cooled (approximately -5 to 0°C). A mixed solution of 6.2 g (8 ml, 0.107 mol) of acetone, 10.8 g (14.8 ml, 0.107 mol) of triethylamine, and 25 ml of acetonitrile was slowly added over 1 hour, and then stirred at room temperature for about 6 hours. 120 ml of pentane was added to the reaction mixture, stirred for 30 minutes, and the upper layer (organic layer) was extracted. This process was repeated 3 times. The solvent of the collected organic layer was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [59℃@3.4torr] to obtain 13.8 g (yield: 52.1%) of N,N-diisopropyl-1,1,2,2-tetramethyl-2-(prop-1-en-2-yloxy)disilan-1-amine as a colorless liquid.

[0076] The characteristic peaks of the NMR analysis results of the product are as follows.

[0077] 1H-NMR(C6D6): δ 0.35 [s, 6H, -Si(CH3)2OC(CH2)CH3], 0.39 [s, 6H, -Si(CH3)2N(CH(CH3)2)2], 1.06-1.08 [d, 12H, -Si(CH3)2N(CH(CH3)2)2], 1.76 [d, 3H, -Si(CH3)2OC(CH2)CH3], 3.13-3.23 [q, 2H, -Si(CH3)2N(CH(CH3)2)2], 4.11-4.12 [t, 1H, -SiOC(CH2)(CH3)], 4.23 [s, 1H, -SiOC(CH2)(CH3)]

[0078] Example 1. Preparation of 1,1,2,2-tetramethyldisilane-1,2-diyl diacetate

[0079] 200 ml of hexane was cooled to a low temperature (approximately 0°C), 20 g (0.107 mol) of 1,2-dichlorotetramethyldisilane was added, and 13.5 g (0.224 mol) of acetic acid was added at a low temperature (approximately -5 to 0°C). While maintaining the low temperature (approximately -5 to 0°C), 22.7 g (0.224 mol) of diethylamine was slowly added over 1 hour, and the mixture was stirred at room temperature for approximately 12 hours. The reactant was filtered, and the solvent of the obtained filtrate was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [35℃@0.1torr] to obtain 15 g (yield: 60%) of 1,1,2,2-tetramethyldisilane-1,2-diyl diacetate, a colorless liquid.

[0080] The NMR analysis results of the product are as shown in Figure 1, and the characteristic peaks are as follows.

[0081] 1H-NMR(C6D6): δ 0.51 [s, 12H, -Si(CH3)2-OCOCH3], 1.68 [s, 6H, -Si(CH3)2-OCOCH3]

[0082] Example 2. Preparation of 1,1,2,2-tetramethyl-1,2-bis(prop-1-en-2-yloxy)disilane

[0083] 200 ml of acetonitrile was cooled to a low temperature (approximately -10°C), and 32.02 g (0.214 mol) of sodium iodide was added. 20 g (0.107 mol) of 1,2-dichlorotetramethyldisilane was added, stirred at room temperature for 1 hour, and then recooled (approximately -5 to 0°C). A mixed solution of 13 g (16.6 ml, 0.224 mol) of acetone, 22.7 g (31.3 ml, 0.224 mol) of triethylamine, and 20 ml of acetonitrile was slowly added over 1 hour, and then stirred at room temperature for approximately 6 hours. 100 ml of pentane was added to the reaction mixture, stirred for 30 minutes, and the upper layer (organic layer) was extracted. This process was repeated five times. The solvent of the collected organic layer was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [54°C@3.9 torr] to obtain 14.7 g (yield: 60%) of 1,1,2,2-tetramethyl-1,2-bis(prop-1-en-2-yloxy)disilane as a colorless liquid.

[0084] The NMR analysis results of the product are as shown in Figure 2, and the characteristic peaks are as follows.

[0085] 1H-NMR(C6D6): δ 0.38 [s, 12H, -Si(CH3)2], 1.73 [d, 6H, -SiOC(CH2)(CH3)J= 0.8Hz], 4.07 [m, 2H, -Si-OC(CH2)(CH3)], 4.19 [d, 2H,-Si-OC(CH2)(CH3) J= 0.8Hz]

[0086] Example 3. Preparation of 1,1,2,2-tetramethyl-1,2-bis((trimethylsilyl)oxy)disilane

[0087] 200 ml of hexane was cooled to a low temperature (approximately 0°C), 20 g (0.107 mol) of 1,2-dichlorotetramethyldisilane was added, and 19.3 g (0.214 mol) of trimethylsilanol was added at a low temperature (approximately -5 to 0°C). While maintaining the low temperature (approximately -5 to 0°C), 21.6 g (0.214 mol) of diethylamine was slowly added over 1 hour, and the mixture was stirred at room temperature for approximately 12 hours. The reactant was filtered, and the solvent of the obtained filtrate was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [59℃@5torr] to obtain 18.9 g (yield: 60%) of 1,1,2,2-tetramethyl-1,2-bis((trimethylsilyl)oxy)disilane)disilane as a colorless liquid.

[0088] The NMR analysis results of the product are as shown in Figure 3, and the characteristic peaks are as follows.

[0089] 1 H-NMR(C6D6): δ 0.15 [s, 18H, -Si(CH3)2-OSi(CH3)3], 0.29 [s, 12H, -Si(CH3)2-OSi(CH3)3]

[0090] Example 4. Preparation of 1-methoxy-1,1,2,2-tetramethyl-2-(prop-1-en-2-yloxy)disilane

[0091] A 60 ml solution of pentane was cooled to a low temperature (approximately -10°C), and 10 g (0.036 mol) of N,N-diisopropyl-1,1,2,2-tetramethyl-2-(prop-1-en-2-yloxy)disilan-1-amine synthesized in Preparation Example 1 was added. 1.4 g (1.77 ml, 0.043 mol) of methanol was slowly added over 10 minutes, and the mixture was stirred at room temperature for approximately 6 hours. The final reaction product was filtered, and the solvent of the obtained filtrate was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [50℃@20torr] to obtain 5.8 g (yield: 77.3%) of 1-methoxy-1,1,2,2-tetramethyl-2-(prop-1-en-2-yloxy)disilane as a colorless liquid.

[0092] The NMR analysis results of the product are as shown in Figure 4, and the characteristic peaks are as follows.

[0093] 1 H-NMR(C6D6): δ 0.27 [s, ​​6H, -Si(CH3)2OCH3], 0.36 [s, 6H, -Si(CH3)2OC(CH2)(CH3)], 1.74 [d, 3H, -Si(CH3)2OC(CH2)(CH3)], 3.29 [s, 3H, -Si(CH3)2OCH3], 4.09-4.10 [t, 1H, -Si(CH3)2OC(CH2)(CH3)], 4.23 [s, 1H, -Si(CH3)2OC(CH2)(CH3)]

[0094] Example 5. Preparation of 2,2,4,4,5,5,7-heptamethyl-3,6-dioxa-2,4,5-trisilaoct-7-ene

[0095] A 60 ml solution of pentane was cooled to a low temperature (approximately -10°C), and 10 g (0.036 mol) of N,N-diisopropyl-1,1,2,2-tetramethyl-2-(prop-1-en-2-yloxy)disilan-1-amine synthesized in Preparation Example 1 was added. 3.95 g (0.043 mol) of trimethylsilanol was slowly added over 10 minutes, and the mixture was stirred at room temperature for approximately 6 hours. The final reaction product was filtered, and the solvent of the obtained filtrate was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [50℃@4torr] to obtain 7.7 g (yield: 80%) of 2,2,4,4,5,5,7-heptapthyl-3,6-dioxa-2,4,5-trisilaoct-7-ene [2,2,4,4,5,5,7-heptamethyl-3,6-dioxa-2,4,5-trisilaoct-7-ene] as a colorless liquid.

[0096] The NMR analysis results of the product are as shown in Figure 5, and the characteristic peaks are as follows.

[0097] 1 H-NMR(C6D6): δ 0.13 [s, 9H, Si-O-Si(CH3)3], 0.30 [s, 6H, -Si(CH3)2OSi (CH3)3], 0.36 [s, 6H, -Si(CH3)2OC(CH2)(CH3)], 1.76 [d, 3H, -Si(CH3)2OC(CH2)(CH3)J= 0.8Hz], 4.09-4.10 [m, 1H, -Si(CH3)2OC(CH2)(CH3)], 4.22-4.23 [d, 1H, -Si(CH3)2OC(CH2)(CH3)J= 0.8Hz]

[0098] Example 6. Preparation of 1,1,1,2,2-pentamethyl-2-(prop-1-en-2-yloxy)disilane

[0099] 30 ml of acetonitrile was cooled to a low temperature (approximately -10°C), and 4.49 g (0.030 mol) of sodium iodide was added. 5 g (0.030 mol) of chloropentamethyldisilane was added, stirred at room temperature for 1 hour, and then recooled (approximately -5 to 0°C). A mixed solution of 1.82 g (2.3 ml, 0.031 mol) of acetone, 3.18 g (4.4 ml, 0.031 mol) of triethylamine, and 5 ml of acetonitrile was slowly added over 1 hour, and then stirred at room temperature for approximately 6 hours. 30 ml of pentane was added to the reaction mixture, stirred for 30 minutes, and the upper layer (organic layer) was extracted. This process was repeated three times. The solvent in the collected organic layer was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [52°C@35 torr] to obtain 6.2 g (yield: 55%) of 1,1,1,2,2-pentamethyl-2-(prop-1-en-2-yloxy)disilane as a colorless liquid.

[0100] The NMR analysis results of the product are as shown in Figure 6, and the characteristic peaks are as follows.

[0101] 1 H-NMR(C6D6): δ 0.13 [s, 9H,-Si(CH3)3], 0.31 [s, 6H, -Si(CH3)2OC(CH2)CH3], 1.73 [d, 3H, -Si(CH3)2OC(CH2)CH3], 4.07-4.08 [t, 1H, -Si(CH3)2OC(CH2)CH3], 4.16 [s, 1H, -Si(CH3)2OC(CH2)CH3]

[0102] Example 7. Preparation of 1,1,1,3,3-pentamethyl-3-(trimethylsilyl)disiloxane

[0103] 50 ml of pentane was cooled to a low temperature (approximately 0°C), 5 g (0.030 mol) of chloropentamethyldisilane was added, and 2.84 g (0.031 mol) of trimethylsilanol was added at a low temperature (approximately -5 to 0°C). While maintaining the low temperature (approximately -5 to 0°C), 3.18 g (0.031 mol) of diethylamine was slowly added over 1 hour, and the mixture was stirred at room temperature for approximately 12 hours. The reactant was filtered, and the solvent of the obtained filtrate was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [50℃@35torr] to obtain 6.6 g (yield: 50%) of 1,1,1,3,3-pentamethyl-3-(trimethylsilyl)disiloxane as a colorless liquid.

[0104] The NMR analysis results of the product are as shown in Figure 7, and the characteristic peaks are as follows.

[0105] 1 H-NMR(C6D6): δ 0.125 [s, 9H, -Si(CH3)2-Si(CH3)3], 0.127 [s, ​​9H, -Si(CH3)2-OSi(CH3)3], 0.247 [s, ​​6H, -Si(CH3)2-Si(CH3)3],

[0106] In addition, the thermogravimetric analysis (TGA) results of the compounds obtained in Examples 1 to 7 of FIG. 8 showed weight changes in the temperature range for forming a silicon-containing thin film, confirming that they exhibited properties suitable for use as precursors for forming thin films.

[0107] While the present invention has been described with reference to preferred embodiments as described above, it is not limited to the above-described embodiments, and various modifications and variations are possible by those skilled in the art without departing from the spirit of the invention. Such modifications and variations are deemed to fall within the scope of the present invention and the appended claims.

Claims

1. A precursor for forming a low dielectric constant silicon-containing thin film, characterized in that it comprises a silicon-containing compound represented by the following chemical formula 1. [Chemical Formula 1] In the above chemical formula 1, R1 to R4 are each independently a hydrogen atom or a C1-C6 straight-chain, branched or cyclic alkyl group, an allyl group containing a C1-C6 straight-chain, branched or cyclic functional group, a vinyl group containing a C1-C6 straight-chain, branched or cyclic functional group, a primary or secondary amine group, or a phenyl group containing or not containing a C1-C6 functional group, X is a functional group that can bond to a silicon atom, Y is any one of the following structural formulas 1 to 3, [Structural formula 1] [Structural formula 2] [Structural formula 3] In the above structural formula 1 or 2, The above R5 to R7 are each independently a hydrogen atom or a C1-C6 straight-chain, branched or cyclic alkyl group, n is an integer from 0 to 3, In the above structural formula 1, Z is NR (wherein, R" is a hydrogen atom or a straight or branched alkyl or alkenyl group of C1-C6), O, S, and any one selected from In the above structural formula 3, R8 to R 10 are each independently a hydrogen atom or a C1-C6 straight-chain, branched or cyclic alkyl group, an allyl group containing a C1-C6 straight-chain, branched or cyclic functional group, a vinyl group containing a C1-C6 straight-chain, branched or cyclic functional group, a primary or secondary amine group, or a phenyl group containing or not containing a C1-C6 functional group.

2. In claim 1, A precursor for forming a low dielectric constant silicon-containing thin film, characterized in that the above X is the same as Y.

3. In claim 1, The above X is different from Y, Hydrogen atom, or C1-C6 straight-chain or cyclic alkyl or alkenyl group, alkoxy group, or -OSiR 11 R 12 R 13 (Here, R 11 Inland R 13 A precursor for forming a low-k silicon-containing thin film, characterized in that each independently represents a hydrogen atom or a C1-C6 straight-chain, branched or cyclic alkyl group, an allyl group containing a C1-C6 straight-chain, branched or cyclic functional group, a vinyl group containing a C1-C6 straight-chain, branched or cyclic functional group, a primary or secondary amine group, or a phenyl group containing or not containing a C1-C6 functional group.

4. In claim 1, A precursor for forming a low-k silicon-containing thin film, characterized in that it additionally contains a solvent.

5. In claim 4, The above solvent is C1-C 16 A precursor for forming a low dielectric constant silicon-containing thin film, characterized in that it is one or more of a saturated or unsaturated hydrocarbon, ketone, ether, glyme, ester, tetrahydrofuran, and tertiary amine.

6. In claim 4, A precursor for forming a low-k silicon-containing thin film, characterized in that the solvent is included in an amount of 1 to 99 wt% based on the total weight of the precursor for forming a low-k silicon-containing thin film.

7. A method for forming a low-k silicon-containing thin film, characterized by including a process for forming a thin film on a substrate using a precursor for forming a low-k silicon-containing thin film according to claim 1 or 4.

8. In claim 7, The process of forming a thin film on the above substrate is: A process of forming a precursor thin film by depositing the precursor for forming the thin film on the surface of a substrate; A process of reacting the above precursor thin film with a reactive gas; A method for forming a low dielectric constant silicon-containing thin film, characterized by including:

9. In claim 8, A method for forming a low dielectric constant silicon-containing thin film, characterized in that the reactive gas is one or more of nitrogen (N2), ammonia (NH3), hydrazine (N2H4), nitrous oxide (N2O), oxygen (O2), water vapor (H2O), ozone (O3), hydrogen peroxide (H2O2), silane (SiH4), hydrogen (H2), and diborane (B2H6).

10. In claim 8, A method for forming a low-k silicon-containing thin film, characterized in that the process for forming the precursor thin film includes a process of vaporizing the precursor for forming the low-k silicon-containing thin film and transporting it into a chamber.

11. In claim 8, A method for forming a low dielectric constant silicon-containing thin film, characterized in that the above deposition is performed by any one of a spin-on dielectric (SOD) process, a low temperature plasma (LTP) process, a chemical vapor deposition (CVD) process, a plasma enhanced chemical vapor deposition (PECVD) process, a high density plasma chemical vapor deposition (HDPCVD) process, an atomic layer deposition (ALD) process, or a plasma enhanced atomic layer deposition (PEALD) process.

12. In claim 7, The process of forming a thin film on the above substrate is: A method for forming a low-k silicon-containing thin film, characterized by comprising a step of supplying a precursor for forming a low-k silicon-containing thin film to a substrate and applying plasma to form a thin film.

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