Precursor for forming low-dielectric constant silicon-containing thin film and method for forming low-dielectric constant silicon-containing thin film by using same

Abstract

The present invention relates to a precursor for forming a low-dielectric constant silicon-containing thin film, the precursor comprising a silicon-containing compound represented by chemical formula 1 or chemical formula 2, and to a method for forming a thin film by using the precursor. The use of a novel siloxane compound containing a vinyl group as a precursor enables the formation of a good-quality silicon-containing thin film, along with an excellent thin film growth rate, when applied to a thin film forming process.

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 siloxane compound containing a novel vinyl group 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 made in consideration of the above-described prior arts, and its purpose is to provide a precursor comprising a siloxane compound containing a novel vinyl group as a precursor compound, which is liquid at room temperature and thus easy to store and handle, and which 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 dielectric constant silicon-containing thin film by using the precursor for forming the low dielectric constant silicon-containing thin film.

[0009] The precursor for forming a low dielectric constant silicon-containing thin film of the present invention to achieve the above purpose is characterized by including a silicon-containing compound represented by the following chemical formula 1 or chemical formula 2.

[0010] [Chemical Formula 1]

[0011]

[0012] [Chemical Formula 2]

[0013]

[0014] In the above chemical formula 1 or chemical formula 2, R1 to R5 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, R6 to R8 are each independently a hydrogen atom or a C1-C6 straight-chain, branched or cyclic alkyl group, X is O or NR' (R' is a hydrogen atom or a C1-C6 straight-chain, branched or cyclic alkyl group), Y is any one selected from NR" (R" is a hydrogen atom or a C1-C6 straight-chain or branched alkyl group or an alkenyl group), O, S, and n is 0. An integer selected from 3.

[0015] At this time, at least one of R1 to R4 in Chemical Formula 1 or Chemical Formula 2 may be a C1-C4 straight-chain or branched alkyl group, and at least one of R7 and R8 in Chemical Formula 2 may be a hydrogen atom. In addition, n in Chemical Formula 1 or Chemical Formula 2 may be 0.

[0016] Additionally, the precursor for forming the low dielectric constant silicon-containing thin film may additionally include a solvent.

[0017] The above solvent is C1-C 16 One 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.

[0018] 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.

[0019] 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.

[0020] 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).

[0021] Additionally, the process of forming the precursor thin film may include a process of vaporizing the precursor for forming the low-k silicon-containing thin film and transporting it into the chamber.

[0022] 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.

[0023] 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.

[0024] The precursor according to the present invention can form a high-quality silicon-containing thin film by including a siloxane compound containing a novel vinyl group as a precursor compound.

[0025] 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).

[0026] Figure 1 is a diagram of the compound obtained in Example 1. 1 This is the result of H-NMR analysis.

[0027] Figure 2 is a diagram of the compound obtained in Example 2. 1 This is the result of H-NMR analysis.

[0028] Figure 3 is a diagram of the compound obtained in Example 3.1 This is the result of H-NMR analysis.

[0029] Figure 4 is a diagram of the compound obtained in Example 4. 1 This is the result of H-NMR analysis.

[0030] Figure 5 shows the TGA measurement results of the compounds obtained in Examples 1 to 4.

[0031] 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.

[0032] The 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 or chemical formula 2.

[0033] [Chemical Formula 1]

[0034]

[0035] [Chemical Formula 2]

[0036]

[0037] In the above chemical formula 1 or chemical formula 2, R1 to R5 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, R6 to R8 are each independently a hydrogen atom or a C1-C6 straight-chain, branched or cyclic alkyl group, X is O or NR' (R' is a hydrogen atom or a C1-C6 straight-chain, branched or cyclic alkyl group), Y is any one selected from NR" (R" is a hydrogen atom or a C1-C6 straight-chain or branched alkyl group or an alkenyl group), O, S, and n is 0. An integer selected from 3.

[0038] The silicon-containing compound represented by the above chemical formula 1 or 2 contains a vinyl ether group, unlike octamethylcyclotetrasiloxane (OMCTS) used as a conventional precursor, and thus can increase the thin film growth rate and thus improve the effectiveness as a precursor.

[0039] In addition, as a specific example of the silicon-containing compound represented by the chemical formula 1 or 2, a chemical structure in which at least one of R1 to R4 in the chemical formula 1 or 2 is a straight-chain or branched alkyl group of C1-C4 may be exemplified, and a chemical structure in which at least one of R7 and R8 in the chemical formula 2 is a hydrogen atom may be exemplified. In addition, a chemical structure in which n is 0 in the chemical formula 1 or 2 may be exemplified.

[0040] The silicon-containing compound represented by the above chemical formula 1 or 2 has a double bond functional group together with a siloxane bond, so it can form a stable Si-O-Si bond through a deposition process, and since it has a large number of silicon terminal methyl groups (-SiMe3, terminal methyl group) compared to the silicon element, it can effectively increase the ratio of silicon terminal methyl groups in the thin film, so it is advantageous for forming a low-k silicon thin film. In addition, the double bond functional group Si-CH x -Si bonds can be formed, so a low-k silicon-containing thin film with a high elastic modulus can be formed.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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).

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] For example, by supplying a precursor gas for forming a low-k silicon-containing thin film, oxygen gas, and a carrier gas, hydrogen 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.

[0051] 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, or a gas containing carbon on the substrate and generating plasma.

[0052] As the above fluorine source, SiF4, which is commonly used, can be used, and as the carbon-containing gas, 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 can be used.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] The effects of the present invention are explained through the following examples.

[0059] Manufacturing Example 1. Manufacturing of N,N-diethyl-1,1-dimethyl-1-(prop-1-en-2-yloxy)silanamine

[0060] 8ℓ of pentane was cooled to a low temperature (approximately 0℃), 500g (3.87mol) of dichlorodimethylsilane was added, and the mixture was cooled to a low temperature (approximately -15 to -5℃). 561g (7.67mol) of diethylamine was slowly added over 2 hours, and the mixture was stirred at room temperature for about 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 [48℃@10torr] to obtain 586g (yield: 91%) of 1-chloro-N,N-diethyl-1,1-dimethylsilanamine as a colorless liquid.

[0061] The characteristic peaks of the NMR analysis results of the product are as follows.

[0062] 1 H-NMR(CDCl3): δ0.46 [s, 6H, -Si(CH3)2], 1.02-1.05 [t, 6H, -SiN(CH2)2(CH3)2], 2.86-2.91 [q, 4H, -SiN(CH2)2(CH3)2]

[0063] 4 ℓ of acetonitrile was cooled to a low temperature (approximately -10 ℃), and 530.3 g (3.54 mol) of sodium iodide was added. 586.4 g of the synthesized 1-chloro-N,N-diethyl-1,1-dimethylsilanamine was added, stirred at room temperature for 1 hour, and then re-cooled (approximately -5 to 0 ℃). A mixed solution of 216 g (275 ml, 3.72 mol) of acetone, 358 g (493 ml, 3.54 mol) of triethylamine, and 0.5 ℓ of acetonitrile was slowly added over 1 hour, and then stirred at room temperature for approximately 6 hours. 600 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 [57°C@10 torr] to obtain 456.3 g (yield: 87.8%) of N,N-diethyl-1,1-dimethyl-1-(prop-1-en-2-yloxy)silanamine as a colorless liquid.

[0064] The characteristic peaks of the NMR analysis results of the product are as follows.

[0065] 1 H-NMR(CDCl3): δ0.18 [s, 6H, -Si(CH3)2], 0.99-1.02 [t, 6H, -SiN(CH2)2(CH3)2], 1.76 [d, 3H, -SiOC(CH2)(CH3)J= 0.8Hz], 2.84-2.90 [q, 4H, -SiN(CH2)2(CH3)2] 4.04 [d, 1H, -SiOC(CH2)(CH3)J= 0.8Hz], 4.06 [s, 1H, -SiOC(CH2)(CH3)]

[0066] Manufacturing Example 2. Manufacturing of 1-((3,3-dimethylbut-1-en-2-yl)oxy)-N,N-diethyl-1,1-dimethyl silanamine

[0067] 8ℓ of pentane was cooled to a low temperature (approximately 0℃), 500g (3.87mol) of dichlorodimethylsilane was added, and the mixture was cooled to a low temperature (approximately -15 to -5℃). 561g (7.67mol) of diethylamine was slowly added over 2 hours, and the mixture was stirred at room temperature for about 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 [48℃@10torr] to obtain 586g (yield: 91%) of 1-chloro-N,N-diethyl-1,1-dimethylsilanamine as a colorless liquid.

[0068] The characteristic peaks of the NMR analysis results of the product are as follows.

[0069] 1 H-NMR(CDCl3): δ0.46 [s, 6H, -Si(CH3)2], 1.02-1.05 [t, 6H, -SiN(CH2)2(CH3)2], 2.86-2.91 [q, 4H, -SiN(CH2)2(CH3)2]

[0070] 150 ml of acetonitrile was cooled to a low temperature (approximately -10°C), and 15.3 g (0.102 mol) of sodium iodide was added. 16.9 g of the synthesized 1-chloro-N,N-diethyl-1,1-dimethylsilanamine was added, stirred at room temperature for 1 hour, and then re-cooled (approximately -5 to 0°C). A mixed solution of 10.21 g (12.7 ml, 0.102 mol) of pinacolone, 10.3 g (14.2 ml, 0.102 mol) of triethylamine, and 20 ml of acetonitrile was slowly added over 1 hour, and 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 5 times. The solvent of the collected organic layer was removed under reduced pressure to obtain 20 g (yield: 85.5%) of 1-((3,3-dimethylbut-1-en-2-yl)oxy)-N,N-diethyl-1,1-dimethylsilanamine] as a colorless liquid.

[0071] The characteristic peaks of the NMR analysis results of the product are as follows.

[0072] 1H-NMR(CDCl3): δ0.18 [s, 6H, -Si(CH3)2], 0.99-1.03 [t, 6H, -SiN(CH2)2(CH3)2], 1.05 [s, 9H,-SiOC=(CH2)C(CH3)3] 1.76 [d, 3H, -SiOC(CH2)(CH3)J= 0.8Hz], 2.84-2.90 [q, 4H, -SiN(CH2)2(CH3)2] 2.856-2.909 [q, 4H, -SiN(CH2CH3)2] 3.941-3.943 [d, 1H, -SiOC(CH2)(CH3)J= 1.2Hz], 4.046-4.049 [d, 1H, -SiOC(CH2)(CH3)J= 1.2Hz]

[0073] Manufacturing Example 3. Manufacturing of N,N-diethyl-1-methyl-1-(prop-1-en-2-yloxy)-1-vinylsilanamine

[0074] 2 ℓ of pentane was cooled to a low temperature (approximately 0 ℃) and 60 g (0.43 mol) of dichloromethylvinylsilane was added, followed by cooling to a low temperature (approximately -15 to -5 ℃). 65.33 g (0.89 mol) of diethylamine was slowly added over 1 hour, and the mixture was stirred at room temperature for about 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 [65.0 ℃ @ 10 torr] to obtain 53 g (yield: 70%) of 1-chloro-N,N-diethyl-1-methyl-1-vinylsilanamine as a colorless liquid.

[0075] The characteristic peaks of the NMR analysis results of the product are as follows.

[0076] 1H-NMR(CDCl3): δ0.507 [s, ​​3H, -Si(CH3)], 1.014-1.049 [t, 6H, -SiN(CH2)2(CH3)2], 2.868-2.920 [q, 4H, -SiN(CH2)2(CH3)2], 5.969-6.144 [m, 3H-SiCH=CH2]

[0077] 150 ml of acetonitrile was cooled to a low temperature (approximately 0°C), and 21.1 g (0.141 mol) of sodium iodide was added. 25 g (0.14 mol) of the synthesized 1-chloro-N,N-diethyl-1-methyl-1-vinylsilanamine was added, stirred at room temperature for 1 hour, and then re-cooled (approximately -5 to 0°C). A mixture of 9.0 g (11.48 ml, 0.16 mol) of acetone, 21.1 g (19.60 ml, 0.14 mol) of triethylamine, and 50 ml of acetonitrile was slowly added over 1 hour, and then stirred at room temperature for about 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 5 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 [70℃@7torr] to obtain 23.6 g (yield: 84%) of N,N-diethyl-1-methyl-1-(prop-1-en-2-yloxy)-1-vinylsilanamine as a colorless liquid.

[0078] The characteristic peaks of the NMR analysis results of the product are as follows.

[0079] 1H-NMR(CDCl3): δ0.254 [s, 3H, -Si(CH3)], 0.991-1.026 [t, 6H, -SiN(CH2CH3)2], 1.786-1.788 [d, 3H, -SiOC(CH2)(CH3)J= 0.8Hz], 2.860-2.913 [q, 4H, -SiN(CH2)2(CH3)2] 4.059-4.061 [d, 1H, -SiOC(CH2)(CH3)J= 0.8Hz], 4.100 [s, 1H, -SiOC(CH2)(CH3)] 5.969-6.144 [m, 3H -SiCH=CH2]

[0080] Manufacturing Example 4. Manufacturing of 1-((3,3-dimethylbut-1-en-2-yl)oxy)-N,N-diethyl-1-methyl-1-vinylsilanamine

[0081] 2ℓ of pentane was cooled to a low temperature (approximately 0℃), 60g (0.43mol) of dichloromethylvinylsilane was added, and then cooled to a low temperature (approximately -15 to -5℃). 65.33g (0.89mol) of diethylamine was slowly added over 1 hour, and the mixture was stirred at room temperature for about 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 [65.0℃@10torr] to obtain 53g (yield: 70%) of 1-chloro-N,N-diethyl-1-methyl-1-vinylsilanamine as a colorless liquid.

[0082] The characteristic peaks of the NMR analysis results of the product are as follows.

[0083] 1H-NMR(CDCl3): δ0.507 [s, ​​3H, -Si(CH3)], 1.014-1.049 [t, 6H, -SiN(CH2)2(CH3)2], 2.868-2.920 [q, 4H, -SiN(CH2)2(CH3)2], 5.969-6.144 [m, 3H-SiCH=CH2]

[0084] 150 ml of acetonitrile was cooled to a low temperature (approximately 0°C), and 33.7 g (0.225 mol) of sodium iodide was added. 40 g (0.225 mol) of the synthesized 1-chloro-N,N-diethyl-1-methyl-1-vinylsilanamine was added, and the mixture was stirred at room temperature for 1 hour. A mixed solution of 24.8 g (31.6 ml, 0.248 mol) of pinacolone, 22.8 g (31.4 ml, 0.225 mol) of triethylamine, and 20 ml of acetonitrile was slowly added over 1 hour, and the mixture was 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 5 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 [89°C@3 torr] to obtain 44.1 g (yield: 82%) of 1-((3,3-dimethylbut-1-en-2-yl)oxy)-N,N-diethyl-1-methyl-1-vinylsilanamine] as a colorless liquid.

[0085] The characteristic peaks of the NMR analysis results of the product are as follows.

[0086] 1H-NMR(CDCl3): δ0.243 [s, 3H, -Si(CH3)], 0.995-1.030 [t, 6H, -SiN(CH2)2(CH3)2], 1.065 [s, 9H, -SiOC=(CH2)C(CH3)3], 2.862-2.920 [m, 4H, -SiN(CH2CH3)2] 3.978-3.981 [d, 1H, -SiOC(CH2)(CH3)J= 1.2Hz], 4.065-4.068 [s, 1H, -SiOC(CH2)(CH3)J= 1.2Hz] 5.846-6.154 [m, 3H -SiCH=CH2]

[0087] Example 1. Preparation of 1,1,1,3,3-pentamethyl-3-(prop-1-en-2-yloxy)disiloxane

[0088] 10 g (0.05 mol) of N,N-diethyl-1,1-dimethyl-1-(prop-1-en-2-yloxy)silanamine synthesized in the above Preparation Example 1 was added to 120 ml of pentane and cooled to a low temperature (approximately -10°C). 4.8 g (0.053 mol) of trimethylsilanol was slowly added over 10 minutes, and the mixture was stirred at room temperature for approximately 6 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 [28℃@5torr] to obtain 7 g (yield: 64%) of 1,1,1,3,3-pentamethyl-3-(prop-1-en-2-yloxy)disiloxane as a colorless liquid.

[0089] The NMR analysis results of the product are as shown in Figure 1, and the characteristic peaks are as follows.

[0090] 1H-NMR(CDCl3): δ0.11 [s, 9H, Si-OSi(CH3)3], 0.16 [s, 6H, -Si(CH3)2], 1.79 [d, 3H, -SiOC(CH2)(CH3),J= 0.4Hz], 4.07 [t, 1H, -SiOC(CH2)(CH3),J= 0.4Hz], 4.14 [s, 1H, -SiOC(CH2)(CH3)]

[0091] Example 2. Preparation of 1-((3,3-dimethylbut-1-en-2-yl)oxy)-1,1,3,3,3-pentamethyl disil-oxane

[0092] 5 g (0.022 mol) of 1-((3,3-dimethylbut-1-en-2-yl)oxy)-N,N-diethyl-1,1-dimethylsilanamine] synthesized in the above Preparation Example 2 was added to 30 ml of pentane and cooled to a low temperature (approximately -10°C). 1.96 g (0.022 mol) of trimethylsilanol was slowly added over 10 minutes, and the mixture was stirred at room temperature for approximately 6 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 [75℃@5torr] to obtain 13g (yield: 75.8%) of 1-((3,3-dimethylbut-1-en-2-yl)oxy)-1,1,3,3,3-pentamethyldisiloxane] as a colorless liquid.

[0093] The NMR analysis results of the product are as shown in Figure 2, and the characteristic peaks are as follows.

[0094] 1H-NMR(CDCl3): δ0.12 [s, 9H, Si-OSi(CH3)3], 0.15 [s, 6H, -Si(CH3)2], 1.06 [s, 9H, -SiOC(CH2)C(CH3)3], 4.04 [d, 1H, -SiOC(CH2)C(CH3)3,J= 1.2Hz], 4.10 [d, 1H, -SiOC(CH2)C(CH3)3,J= 1.2Hz]

[0095] Example 3. Preparation of 1,1,1,3-tetramethyl-3-(prop-1-en-2-yloxy)-3-vinyldisiloxane

[0096] 5.5 g (0.028 mol) of N,N-diethyl-1-methyl-1-(prop-1-en-2-yloxy)-1-vinylsilanamine synthesized in the above Preparation Example 3 was added to 50 ml of pentane and cooled to a low temperature (approximately -10°C). 2.74 g (0.03 mol) of trimethylsilanol was added and stirred at room temperature for approximately 6 hours. The solvent of the reactant was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [70℃@66torr] to obtain 3.9 g (yield: 66%) of 1,1,1,3-tetramethyl-3-prop-1-phen-2-yloxy)-3-vinyldisiloxane [1,1,1,3-tetramethyl-3-(prop-1-en-2-yloxy)-3-vinyldisiloxane] as a colorless liquid.

[0097] The NMR analysis results of the product are as shown in Figure 3, and the characteristic peaks are as follows.

[0098] 1H-NMR(CDCl3): δ0.126 [s, 9H, -OSi(CH3)], 0.228 [s, 3H, -Si(CH3)], 1.793-1.8794 [d, 3H, -SiOC(CH2)(CH3)]), 4.075-4.079 [t, 1H, -SiOC(CH2)(CH3)], 4.159 [s, 1H, -SiOC(CH2)(CH3)], 5.832-6.067 [m, 3H -SiCH=CH2]

[0099] Example 4. Preparation of 1-((3,3-dimethylbut-1-en-2-yl)oxy)-1,3,3,3-tetramethyl-1-vinyldisiloxane

[0100] 10 g (0.041 mol) of 1-((3,3-dimethylbut-1-en-2-yl)oxy)-N,N-diethyl-1-methyl-1-vinylsilanamine] synthesized in the above Preparation Example 4 was added to 50 ml of pentane and cooled to low temperature (approximately -10°C). After adding 4.11 g (0.041 mol) of trimethylsilanol, the mixture was stirred at room temperature for approximately 12 hours. The solvent of the reactant was removed under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [80℃@5torr] to obtain 8.3 g (yield: 77%) of 1-((3,3-dimethylbut-1-en-2-yl)oxy)-1,3,3,3-tetramethyl-1-vinyldisiloxane] as a colorless liquid.

[0101] The NMR analysis results of the product are as shown in Figure 4, and the characteristic peaks are as follows.

[0102] 1H-NMR(CDCl3): δ0.126 [s, 9H, -OSi(CH3)], 0.217 [s, ​​3H, -Si(CH3)], 1.061 [s, 9H, -SiOC(CH2)C(CH3)3]), 4.4065-4.068 [d, 1H, -SiOC(CH2)(CH3)], 4.111-4.1115 [s, 1H, -SiOC(CH2)(CH3)], 5.832-6.067 [m, 3H -SiCH=CH2]

[0103] As a result of the TGA measurement for Examples 1 to 4, as shown in Fig. 5, weight loss was observed without residue in the region below 120°C, and it was found that the high volatility could have a beneficial effect on the deposition process.

[0104] 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 comprising a silicon-containing compound represented by the following chemical formula 1 or chemical formula 2. [Chemical Formula 1] [Chemical Formula 2] In the above chemical formula 1 or chemical formula 2, R1 to R5 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, R6 to R8 are each independently a hydrogen atom or a C1-C6 straight-chain, branched or cyclic alkyl group, X is O or NR' (R' is a hydrogen atom or a straight, branched or cyclic alkyl group of C1-C6), Y is one selected from NR (R is a hydrogen atom or a straight or branched alkyl group or alkenyl group of C1-C6), O, S, n is an integer selected from 0 to 3.

2. In claim 1, A precursor for forming a low dielectric constant silicon-containing thin film, characterized in that at least one of R1 to R4 in chemical formula 1 or chemical formula 2 is a straight-chain or branched alkyl group of C1-C4.

3. In claim 1, A precursor for forming a low-k silicon-containing thin film, characterized in that at least one of R7 and R8 in chemical formula 2 is a hydrogen atom.

4. In claim 1, A precursor for forming a low-k silicon-containing thin film, characterized in that n is 0.

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

6. In claim 5, 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.

7. In claim 5, 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.

8. 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 any one of claims 1 to 7.

9. In claim 8, 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:

10. In claim 9, 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).

11. In claim 9, 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.

12. In claim 9, 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.

13. In claim 8, 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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