Precursor for forming low-k boron nitride-containing thin film and method for forming low-k boron nitride-containing thin film using same

Abstract

The present invention relates to a precursor for forming a boron nitride-containing thin film having a low dielectric constant (low-k) characteristics and a method for forming low-k boron nitride-containing thin film using same and, more specifically, to a precursor capable of forming a high-quality low-k thin film by using a compound having a novel structure containing an amidinate group as a precursor for forming a boron nitride-containing thin film, and to a method for forming a boron nitride-containing thin film using the precursor.

Description

Precursor for forming a low dielectric constant boron nitride-containing thin film and method for forming a low dielectric constant boron nitride-containing thin film using the same

[0001] The present invention relates to a precursor for forming a boron nitride-containing thin film having low-k dielectric constant characteristics and a method for forming a low-k dielectric constant boron nitride-containing thin film using the same. More specifically, the invention relates to a precursor capable of forming a high-quality low-k dielectric constant thin film by using a compound with a novel structure containing an amidinate group as a precursor for forming a boron nitride-containing thin film, and a method for forming a boron nitride-containing thin film using said precursor.

[0002] As integration density improves through the miniaturization and linewidth refinement of semiconductor devices, parasitic capacitance increases, leading to response speed delay (RC delay). Consequently, research and development is underway to address this issue. This parasitic capacitance primarily occurs when metal wirings are placed very close together, resulting in their arrangement having a structure identical to that of a capacitor. To reduce this, it is necessary to form the interlayer insulating film between the metal wirings using an insulating material with a low dielectric constant. Furthermore, securing a sensing margin is essential for reading data stored in the capacitor effectively, and research and development is being conducted to achieve this. The capacitor is typically formed with a structure in which it lands on a storage node contact formed between a standard bit line, and the storage node contact contact contacts the substrate. In this case, parasitic capacitance may occur between the bit line and the storage node contact, or between the bit lines themselves. To reduce this, it is necessary to form an insulating film with a low dielectric constant between the bit line and the storage node contact, or between the bit lines.

[0003] The insulating film 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 silicon-containing thin films such as fluorinated silicate glass (FSG), silicon oxide film containing carbon (SiCO), silicon nitride film (SiN), and silicon nitride film containing carbon (SiCN).

[0004] Precursors conventionally used to form low dielectric constant thin films include octamethylcyclotetrasiloxane (OMCTS), diethoxymethylsilane (DEMS), and tetraethoxyorthosilicate (TEOS). Although the silicon-containing precursors are advantageous for vaporization during the deposition process in liquid form, they have limitations in their scope of application due to issues such as deterioration in etch resistance resulting from the low density of the formed thin film, or difficulty in obtaining a sufficient elastic modulus and low dielectric constant in the formed thin film.

[0005] To solve these problems, technology utilizing boron nitride-containing thin films as insulating films is currently being researched. To manufacture such boron-containing thin films, it is necessary to develop boron-containing compounds suitable for this purpose.

[0006] The present invention has been devised in consideration of the prior art described above, and aims to provide a precursor that includes a novel nitrogen and boron-containing compound having high thermal stability having an amidinate group, is liquid at room temperature, is easy to store and handle, and can form a high-quality low dielectric constant thin film.

[0007] In addition, the purpose is to provide a method for forming a thin film that can form a low dielectric constant boron nitride-containing thin film using the above precursor.

[0008] The objectives of the present invention are not limited to those mentioned above, and other objectives and advantages of the present invention not mentioned may be understood from the following description and will be more clearly understood by the embodiments of the present invention. Furthermore, it will be readily apparent that the objectives and advantages of the present invention can be realized by the means and combinations thereof set forth in the claims.

[0009] To achieve the above objective, according to one embodiment of the present invention, a precursor for forming a low dielectric constant boron nitride-containing thin film comprising a nitrogen and boron-containing compound represented by the following chemical formula 1 can be provided.

[0010] <Chemical Formula 1>

[0011]

[0012] In the above chemical formula 1,

[0013] R1 to R3 may each independently be one of a hydrogen atom, a C1-C6 straight-chain alkyl group, a C2-C6 straight-chain alkenyl group, a C3-C6 branched alkyl group, a C3-C6 branched alkenyl group, a C3-C6 cyclic alkyl group, and a C3-C6 cyclic alkenyl group; R4 and R5 may each independently be selected from a hydrogen atom, a C1-C6 straight-chain alkyl group, a C2-C6 straight-chain alkenyl group, a C3-C6 branched alkyl group, a C3-C6 branched alkenyl group, a C3-C6 cyclic alkyl group, a C3-C6 cyclic alkenyl group, N(R6)(R7), and O(R8); and R6 to R8 may each independently be a hydrogen atom, a C1-C6 straight-chain alkyl group, a C2-C6 straight-chain It may be one of an alkenyl group, a C3-C6 branched alkyl group, a C3-C6 branched alkenyl group, a C3-C6 cyclic alkyl group, and a C3-C6 cyclic alkenyl group, and optionally, R4 and R5 may bond to each other to form a ring structure.

[0014] According to another aspect of the present invention, a method for forming a low dielectric constant boron nitride-containing thin film can be provided, characterized by including a process of forming a thin film on a substrate using a precursor for forming a low dielectric constant boron nitride-containing thin film comprising a compound represented by Formula 1.

[0015] According to another aspect of the present invention, a low dielectric constant boron nitride-containing thin film can be provided by the method for forming a low dielectric constant boron nitride-containing thin film of the present invention.

[0016] The precursor according to the present invention comprises a nitrogen and boron-containing compound containing an amidinate group represented by Chemical Formula 1, thereby enabling the formation of a high-quality boron nitride-containing thin film.

[0017] In addition, by using the above-mentioned precursor for forming a low dielectric constant boron nitride-containing thin film, a low dielectric constant boron nitride-containing thin film having a high elastic modulus or improved etch resistance can be formed, thereby providing a method for forming a thin film that can be utilized for purposes such as next-generation semiconductor insulating films.

[0018] In addition to the effects described above, the effects of the present invention are described together with the details for implementing the invention below.

[0019] FIG. 1 is of the compound prepared in Example 1 of the present invention. 1 This is a graph of the H-NMR analysis results.

[0020] FIG. 2 is of the compound prepared in Example 1 of the present invention. 11 This is a graph of the B-NMR analysis results.

[0021] FIG. 3 is of the compound prepared in Example 2 of the present invention. 1 This is a graph of the H-NMR analysis results.

[0022] FIG. 4 is of the compound prepared in Example 2 of the present invention. 11 This is a graph of the B-NMR analysis results.

[0023] FIG. 5 is of the compound prepared in Example 3 of the present invention. 1 This is a graph of the H-NMR analysis results.

[0024] FIG. 6 is of the compound prepared in Example 3 of the present invention. 11 This is a graph of the B-NMR analysis results.

[0025] FIG. 7 is of the compound prepared in Example 4 of the present invention. 1 This is a graph of the H-NMR analysis results.

[0026] FIG. 8 is of the compound prepared in Example 4 of the present invention. 11 This is a graph of the B-NMR analysis results.

[0027] FIG. 9 is a graph of the thermogravimetric analysis (TGA) results of the compounds prepared in Examples 1 to 4 of the present invention.

[0028] The aforementioned objectives, features, and advantages are described in detail below with reference to this specification, and accordingly, a person skilled in the art to which the present invention pertains will be able to easily implement the technical concept of the present invention. In describing the present invention, detailed descriptions of known technologies related to the present invention are omitted if it is determined that such descriptions may unnecessarily obscure the essence of the present invention.

[0029] Where terms such as "comprising," "having," "containing," "arranging," or "having" are used for a component in this specification, other parts may be added unless "only" is used. Where a component is expressed in the singular, it includes cases where it is included in the plural unless specifically stated otherwise.

[0030] Throughout this specification, unless specifically stated otherwise, each component may be singular or plural.

[0031] Throughout this specification, "A and / or B" means A, B, or A and B unless specifically stated otherwise, and "C to D" means C or more and D or less unless specifically stated otherwise.

[0032] Unless otherwise specifically stated in this specification, the standard of any unit is interpreted to mean "weight."

[0033] In interpreting the components in this specification, they are interpreted to include an error range even if there is no separate explicit description.

[0034] The present invention will be described in more detail below. Terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0035] The precursor for forming a low dielectric constant boron nitride-containing thin film according to the present invention may include a nitrogen and boron-containing compound represented by the following chemical formula 1.

[0036] <Chemical Formula 1>

[0037]

[0038] In the above chemical formula 1,

[0039] R1 to R3 may each independently be one of a hydrogen atom, a C1-C6 straight-chain alkyl group, a C2-C6 straight-chain alkenyl group, a C3-C6 branched alkyl group, a C3-C6 branched alkenyl group, a C3-C6 cyclic alkyl group, and a C3-C6 cyclic alkenyl group; R4 and R5 may each independently be selected from a hydrogen atom, a C1-C6 straight-chain alkyl group, a C2-C6 straight-chain alkenyl group, a C3-C6 branched alkyl group, a C3-C6 branched alkenyl group, a C3-C6 cyclic alkyl group, a C3-C6 cyclic alkenyl group, N(R6)(R7) and O(R8); and R6 to R8 may each independently be a hydrogen atom, a C1-C6 straight-chain alkyl group, a C2-C6 straight-chain It may be one of an alkenyl group, a C3-C6 branched alkyl group, a C3-C6 branched alkenyl group, a C3-C6 cyclic alkyl group, and a C3-C6 cyclic alkenyl group, and optionally, R4 and R5 may be combined with each other to form a ring structure. For example, if R4 and R5 are each selected as ethyl groups, which are C2 straight-chain alkyl groups, the ethyl groups are combined to form a ring structure together with boron (B). According to one example, R4 and R5 may each be independently selected from N(R6)(R7).

[0040] According to one example, R4 and R5 of the above chemical formula 1 may be the same.

[0041] The nitrogen and boron-containing compound represented by the above chemical formula 1 is a precursor with high thermal stability containing an amidinate group, which can have an advantageous effect in forming a high-quality insulating film.

[0042] The nitrogen and boron-containing compound represented by the above chemical formula 1 may include various chemical structures, but may be a compound represented by the following chemical formula 2 as an exemplary chemical structure.

[0043] Chemical formula 2 below represents a structure in which adjacent groups among R6 and R7 are bonded to each other to form a ring structure, and more specifically, a structure in which a cycloaliphatic ring is formed.

[0044] <Chemical Formula 2>

[0045]

[0046] In the above chemical formula 2, X and Y may be the same or different from each other, and each may be independently selected from N, O and C, and n may be an integer from 1 to 3.

[0047] According to one example, the above n can be an integer from 1 to 2, and for example, n can be 2.

[0048] According to one example, the precursor compound represented by the above chemical formula 1 may include, but is not limited to, the following precursor compounds:

[0049] (2-ethyl-N,N´-diethylamidinato)bis(dimethylamino)borane((2-ethyl-N,N-diethylamidinato)bis(dimethylamino)borane, (Et2Et-AMD)B(DMA)2);

[0050] (2-methyl-N,N´-diisopropylamidinato)bis(dimethylamino)borane((2-methyl-N,N-diisopropylamidinato)bis(dimethylamino)borane, (iPr2Me-AMD)B(DMA)2);

[0051] (2-ethyl-N,N-diethylamidinato)(N,N´-dimethylethylenediamino)borane (2-ethyl-N,N-diethylamidinato)(N,N-dimethylethylenediamino)borane, (Et2Et-AMD)B(DMA-EDA)); and

[0052] N-ethyl-2-isobutyl-N-propylamidinato)bis(dimethylamino)borane (N-ethyl-2-isobutyl-N-propylamidinato)bis(dimethylamino)borane, (EtPrisoBu-AMD)B(DMA)2).

[0053] The compound represented by the above chemical formula 1 may be in a liquid state at room temperature, and even if it is in a solid state, it can be converted into a liquid state by dissolving it in a solvent.

[0054] According to one example, the precursor for forming a low dielectric constant boron nitride-containing thin film may additionally include a solvent.

[0055] According to one example, the solvent may include one or more of C1-C16 saturated or unsaturated hydrocarbons, ketones, ethers, glymes, esters, tetrahydrofurans, and tertiary amines, but is not limited thereto. For example, examples of C1-C16 saturated or unsaturated hydrocarbons may include hexane, toluene, heptane, etc., and examples of tertiary amines may include triethylamine, pyridine, etc.

[0056] According to one example, when the total weight of the precursor for forming a thin film containing low dielectric constant boron nitride is 100 weight%, the solvent may be included in an amount of 1 to 99 weight%.

[0057] In particular, it is desirable to include a solvent capable of dissolving the nitrogen and boron-containing compounds when they form a solid state at room temperature or slightly higher. That is, when the solvent is included, the solvent is contained in an amount capable of dissolving the nitrogen and boron-containing compounds, and when the total weight of the precursor for forming a low dielectric constant boron nitride-containing thin film is 100 weight%, the solvent may be included in an amount of 1 to 99 weight%.

[0058] Since the precursor, whether or not it contains the above solvent, is capable of vaporization, it can be supplied into the reactor chamber in the form of a precursor gas. Therefore, depending on the type of nitrogen and boron-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.

[0059] By using such a precursor of the present invention, the present invention can provide a method for forming a low dielectric constant boron nitride-containing thin film, and the method for forming a low dielectric constant boron nitride-containing thin film may include a process of forming a thin film on a substrate using the precursor for forming a low dielectric constant boron nitride-containing thin film.

[0060] According to one example, a process for forming a thin film on the substrate may include the step of supplying a precursor for forming the thin film to the surface of the substrate; and the step of reacting the precursor for forming the thin film with a reactive gas.

[0061] According to one example, the reactive gas may include 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), but is not limited thereto.

[0062] According to one example, the step of supplying the thin film forming precursor to the surface of the substrate may be performed by vaporizing the low dielectric constant boron nitride-containing thin film forming precursor and supplying it into the reactor chamber.

[0063] According to one example, the process of forming a thin film on the substrate may be performed by supplying the low dielectric constant boron nitride-containing thin film forming precursor to the substrate and applying plasma to form the thin film.

[0064] Specifically, the thin film formation process may be performed by a process selected from among 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, and a Plasma Enhanced Atomic Layer Deposition (PEALD) process, or by an application process based thereon.

[0065] In addition, an additional precursor may be introduced for the purpose of improving the properties of the insulating film. The additional precursor may be composed of a central metal that is the same as or different from the precursor for forming a boron nitride-containing thin film according to the present invention.

[0066] The process for forming the thin film can be performed under chamber pressure conditions of 0.1 to 10 Torr. Additionally, for forming plasma within the chamber, the source power may be 50 to 9,000 W, and the bias power may be 0 to 5,000 W. Furthermore, the bias power may not be applied in some cases.

[0067] Due to the structural characteristics of the nitrogen and boron-containing compound represented by Chemical Formula 1 used in the thin film formation process of the present invention, it has high thermal stability, so the thin film formation process is possible over a wide temperature range.

[0068] In addition, a thin film containing low dielectric constant boron nitride can be manufactured by applying the above thin film formation process. The thin film obtained according to the thin film formation method of the present invention may be a thin film containing low dielectric constant amorphous boron nitride. In addition, the thin film obtained according to the thin film formation method of the present invention may have a dielectric constant of 1.5 to 4.0. The dielectric constant may preferably be 1.8 to 3.8, and more preferably 2.0 to 3.5.

[0069] According to one example, the thin film has a density of 1.5 g / cm³ calculated by X-ray reflectance measurement (XRR). 3 It may be above. The above density is preferably 1.7 g / cm³ 3 Ideally, 1.8 g / cm³ 3 It could be more than that.

[0070] The above low dielectric constant boron nitride-containing thin film can form an insulating film, thereby reducing parasitic capacitance between wirings of a semiconductor device and enabling the formation of a high-quality semiconductor device.

[0071] As such, the thin film obtained by applying the thin film formation method of the present invention can exhibit excellent physical properties. Therefore, since a high-quality, low-dielectric constant thin film can be obtained through such a thin film, it can be utilized in next-generation semiconductor devices.

[0072] The structure and operation of the present invention will be described in more detail below through preferred embodiments. However, these are presented as preferred examples of the present invention and should not be interpreted in any way as limiting the present invention.

[0073] [Example 1]

[0074] Preparation of (2-ethyl-N,N-diethylamidinato)bis(dimethylamino)borane [(Et2Et-AMD)B(DMA)2]

[0075] 5.9 g (0.04 mol) of tris(dimethylamino)borane [TDMAB] was diluted with 30 ml of hexane in reaction vessel 1 and cooled to cryogenic temperature (approx. -20°C), then 2 ml (0.02 mol) of tribromoboron (BBr3) was added and stirred at room temperature for about 6 hours. 7.98 g (0.06 mol) of 2-ethyl-N,N-diethylamidinate was diluted with 30 ml of hexane in reaction vessel 2 and cooled to cryogenic temperature (approx. -20°C), then 24.9 ml (0.06 mol) of 2.5 M n-butyl lithium (nBuLi) was slowly added and stirred at room temperature for about 6 hours. After recooling reaction vessel No. 1 to cryogenic temperature (approx. -20℃), the solution from reaction vessel No. 2 was slowly transferred and added, and the mixture was stirred at room temperature for approximately 12 hours. The reaction mixture 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 [73.5℃ @ 1 torr] to obtain 8.5 g (yield: 61%) of (2-ethyl-N,N-diethylamidinato)bis(dimethylamino)borane [(2-ethyl-N,N-diethylamidinato)bis(dimethylamino)borane, (Et2Et-AMD)B(DMA)2], which is a colorless liquid.

[0076] product of 1 H-NMR analysis results are in Fig. 1 and 11 The B-NMR analysis results are as shown in Figure 2, and the target compound was confirmed to have been synthesized by identifying the following characteristic peaks:

[0077] 1H-NMR(C6D6): δ 0.96 [t, 3H, (CH3CH2)N-C(CH2CH3)-N(CH2CH3)], 1.36 [t, 6H, (CH3CH2)N-C(CH2CH3)-N(CH2CH3)], 2.13 [q, 2H, (CH3CH2)N-C(CH2CH3)-N(CH2CH3)], 2.44 [s, 12H, B(N(CH3)2)2], 3.49 [q, 4H, (CH3CH2)N-C(CH2CH3)-N(CH2CH3)]

[0078] 11 B-NMR: δ 28.09 ppm.

[0079] [실시예 2]

[0080] (2-methyl-N,N-diisopropylamidinato)bis(dimethylamino)borane [(iPr2Me-AMD)B(DMA)2]의 제조

[0081] 5.9 g (0.04 mol) of tris(dimethylamino)borane [TDMAB] was diluted with 20 ml of hexane in reaction vessel 1 and cooled to cryogenic temperature (approx. -20°C), then 2 ml (0.02 mol) of tribromoboron (BBr3) was added and stirred at room temperature for about 6 hours. 7.86 g (0.06 mol) of N,N-diisopropylcarbodiimide was diluted with 20 ml of hexane in reaction vessel 2 and cooled to cryogenic temperature (approx. -20°C), then 42.8 ml (0.06 mol) of 1.6 M methyl lithium (MeLi) was slowly added and stirred at room temperature for about 6 hours. After recooling reaction vessel 1 to cryogenic temperature (approx. -20℃), the solution from reaction vessel 2 was slowly transferred and added, and the mixture was stirred at room temperature for approximately 12 hours. The reaction mixture 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 [82.5℃ @ 1 torr] to obtain 7.5 g (yield: 50%) of (2-methyl-N,N-diisopropylamidinato)bis(dimethylamino)borane [(2-methyl-N,N-diisopropylamidinato)bis(dimethylamino)borane, (iPr2Me-AMD)B(DMA)2], which is a colorless liquid.

[0082] product of 1 The H-NMR analysis results are in Figure 3 and 11 The B-NMR analysis results are as shown in Figure 4, and the target compound was confirmed to have been synthesized by identifying the following characteristic peaks:

[0083] 1H-NMR(C6D6): δ 1.31 [d, 12H, ((CH3)2CH)NC(CH3)-N(CH(CH3)2)], 1.60 [s, 3H, ((CH3)2CH)NC(CH3)-N(CH(CH3)2)], 2.43 [s, 12H, B(N(CH3)2)2], 4.05 [m, 2H, ((CH3)2CH)NC(CH3)-N(CH(CH3)2)]

[0084] 11 B-NMR: δ 28.07 ppm.

[0085] [Example 3]

[0086] Preparation of (2-ethyl-N,N-diethylamidinato)(N,N-dimethylethylenediamino)borane [(Et2Et-AMD)B(DMA-EDA)]

[0087] 79 ml (0.56 mol) of triethylamine was diluted with 200 ml of hexane and cooled to a low temperature (approx. 0°C). A solution of 26.9 ml (0.28 mol) of tribromoboron (BBr3) diluted with 40 ml of hexane was added, and the mixture was stirred at room temperature for about 2 hours. A solution of 25 g (0.28 mol) of N,N-dimethylethylenediamine diluted with 100 ml of hexane was added, and the mixture was heated and stirred for about 3 hours. The reaction mixture 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 [51.5℃ @40torr] to obtain 23g (yield: 69%) of colorless liquid 2-bromo-1,3-dimethyl-1,3,2-diazaborolane.

[0088] The above intermediate 1 H-NMR and 11 The B-NMR analysis results were as follows:

[0089] 1H-NMR(C6D6): δ 2.49 [s, 6H, -(CH3)N-CH2CH2-N(CH3)-], 2.76 [s, 4H, -(CH3)N-CH2CH2-N(CH3)-]

[0090] 11 B-NMR: δ 26.32 ppm.

[0091] 3.62 g (0.02 mol) of 2-ethyl-N,N-diethylamidinate was diluted with 30 ml of hexane in reaction vessel No. 2 and cooled to cryogenic temperature (approx. -20°C), then 11.3 ml (0.02 mol) of 2.5 M n-butyl lithium (nBuLi) was slowly added and stirred at room temperature for about 6 hours. 5 g (0.02 mol) of the above 2-bromo-1,3-dimethyl-1,3,2-diazaborolane was diluted with 10 ml of hexane in reaction vessel 1 and cooled to cryogenic temperature (approx. -20°C). Then, the solution from reaction vessel 2 was slowly transferred and added, and the mixture was stirred at room temperature for approximately 12 hours. The reaction mixture 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 [63.3℃@1torr] to obtain 3.6g (yield: 60%) of colorless liquid (2-ethyl-N,N-diethylamidinato)(N,N-dimethylethylenediamino)borane [(2-ethyl-N,N-diethylamidinato)(N,N-dimethylethylenediamino)borane, (Et2Et-AMD)B(DMA-EDA)].

[0092] product of 1 The H-NMR analysis results are in Figure 5 and 11 The B-NMR analysis results are as shown in Figure 6, and the target compound was confirmed to have been synthesized by identifying the following characteristic peaks:

[0093] 1H-NMR(C6D6): δ 1.01 [t, 3H, (CH3CH2)N-C(CH2CH3)-N(CH2CH3)], 1.35 [t, 6H, (CH3CH2)N-C(CH2CH3)-N(CH2CH3)], 2.19 [q, 2H, (CH3CH2)N-C(CH2CH3)-N(CH2CH3)], 2.42 [s, 6H, -(CH3)N-CH2CH2-N(CH3)-], 2.88 [s, 4H, -(CH3)N-CH2CH2-N(CH3)-], 3.52 [q, 4H, (CH3CH2)N-C(CH2CH3)-N(CH2CH3)]

[0094] 11 B-NMR: δ 28.31 ppm

[0095] [실시예 4]

[0096] (N-ethyl-2-isobutyl-N-propylamidinato) bis(dimethylamino)borane [(EtPrisoBu-AMD)B(DMA)2]의 제조

[0097] 5.9 g (0.04 mol) of tris(dimethylamino)borane [TDMAB] was diluted with 15 ml of hexane in reaction vessel 1 and cooled to cryogenic temperature (about -20°C), then 2 ml (0.02 mol) of tribromoboron (BBr3) was added and stirred at room temperature for about 6 hours. 10.6 g (0.06 mol) of N-ethyl-2-isobutyl-N-propylamidinate was diluted with 30 ml of hexane in reaction vessel 2 and cooled to cryogenic temperature (approx. -20°C). Then, 24.9 ml (0.06 mol) of 2.5 M n-butyl lithium (nBuLi) was slowly added, and the mixture was stirred at room temperature for about 6 hours. Reaction vessel 1 was re-cooled to cryogenic temperature (approx. -20°C), the solution from reaction vessel 2 was slowly transferred and added, and the mixture was stirred at room temperature for about 12 hours. The reaction mixture was filtered, and the solvent was removed from the obtained filtrate under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure [83.7℃ @0.1torr] to obtain 12.4g (yield: 74%) of the colorless liquid (N-ethyl-2-isobutyl-N-propylamidinato)bis(dimethylamino)borane [(N-ethyl-2-isobutyl-N-propylamidinato)bis(dimethylamino)borane, (EtPrisoBu-AMD)B(DMA)2].

[0098] product of 1 The H-NMR analysis results are in Fig. 7 and 11 The B-NMR analysis results are as shown in Figure 8, and the target compound was confirmed to have been synthesized by identifying the following characteristic peaks:

[0099] 1H-NMR(C6D6): δ 0.90 [d, 6H, (CH3CH2)NC(CH2CH(CH3)2-N(CH2CH2CH3)], 1.06 [t, 3H, (CH3CH2)NC(CH2CH(CH3)2-N(CH2CH2CH3)], 1.33 [t, 3H, (CH3CH2)NC(CH2CH(CH3)2-N(CH2CH2CH3)], 1.82 [m, 3H, (CH3CH2)NC(CH2CH(CH3)2-N(CH2CH2CH3)], 2.11 [d, 2H, (CH3CH2)NC(CH2CH(CH3)2-N(CH2CH2CH3)], 2.45 [s, 12H, B(N(CH3)2)2], 3.41 [t, 2H, (CH3CH2)NC(CH2CH(CH3)2-N(CH2CH2CH3)], 3.49 [q, 2H, (CH3CH2)NC(CH2CH(CH3)2-N(CH2CH2CH3)]

[0100] 11 B-NMR: δ 28.25 ppm.

[0101] Table 1 below lists the structure, weight-average molecular weight (Mw) value, visually observed phase (@25℃), and thermogravimetric analysis (TGA) results of the compounds obtained in Examples 1 to 4, and Figure 9 shows the TGA results graph of the compounds obtained in Examples 1 to 4. From these results, it was confirmed that high vapor pressure and low residual amount were observed, indicating properties suitable for use as a precursor for forming boron nitride-containing thin films.

[0102] [Table 1]

[0103]

[0104] Although the present invention has been described in more detail with reference to preferred embodiments and drawings as described above, this specification is not necessarily limited to these embodiments. Various modifications and changes can be made by those skilled in the art within the scope of the technical spirit of this specification, and such modifications and changes should be considered to fall within the scope of the appended claims of this specification. Accordingly, the embodiments and drawings disclosed in this specification are intended to explain, not limit, the technical spirit of this specification, and the scope of the technical spirit of this specification is not limited by these embodiments. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. The scope of protection of this specification should be interpreted by the claims, and all technical spirits within an equivalent scope should be interpreted as being included within the scope of rights of this specification.

Claims

1. A precursor for forming a low dielectric constant boron nitride-containing thin film comprising a nitrogen and boron-containing compound represented by the following chemical formula 1: <Chemical Formula 1> In the above chemical formula 1, R1 to R3 are each independently one of a hydrogen atom, a C1-C6 straight-chain alkyl group, a C2-C6 straight-chain alkenyl group, a C3-C6 branched alkyl group, a C3-C6 branched alkenyl group, a C3-C6 cyclic alkyl group, and a C3-C6 cyclic alkenyl group, and R4 and R5 are each independently selected from a hydrogen atom, a C1-C6 straight-chain alkyl group, a C2-C6 straight-chain alkenyl group, a C3-C6 branched alkyl group, a C3-C6 branched alkenyl group, a C3-C6 cyclic alkyl group, a C3-C6 cyclic alkenyl group, N(R6)(R7) and O(R8). R6 to R8 are each independently one of a hydrogen atom, a C1-C6 straight-chain alkyl group, a C2-C6 straight-chain alkenyl group, a C3-C6 branched alkyl group, a C3-C6 branched alkenyl group, a C3-C6 cyclic alkyl group, and a C3-C6 cyclic alkenyl group, and Optionally, R4 and R5 can combine to form a ring structure.

2. In Paragraph 1, The above R4 and R5 are each independently selected from N(R6)(R7), precursors for forming a low dielectric constant boron nitride-containing thin film.

3. In Paragraph 1, The above R4 and R5 are selected as the same precursor for forming a low dielectric constant boron nitride-containing thin film.

4. In Paragraph 1, A precursor for forming a low dielectric constant boron nitride-containing thin film, wherein the above chemical formula 1 is represented by the following chemical formula 2: <Chemical Formula 2> In the above chemical formula 2, X and Y are identical or different from each other and are each one of N, O and C, and n is an integer from 1 to 3.

5. In Paragraph 4, A precursor for forming a low dielectric constant boron nitride-containing thin film, where n is an integer from 1 to 2.

6. In Paragraph 1, A precursor for forming a low dielectric constant boron nitride-containing thin film, further comprising a solvent.

7. In Paragraph 6, The above solvent is a precursor for forming a low dielectric constant boron nitride-containing thin film, comprising one or more of C1-C16 saturated or unsaturated hydrocarbons, ketones, ethers, glymes, esters, tetrahydrofurans, and tertiary amines.

8. In Paragraph 6, A precursor for forming a low dielectric constant boron nitride-containing thin film, wherein the solvent is included in an amount of 1 to 99 weight% when the total weight of the precursor for forming a low dielectric constant boron nitride-containing thin film is 100 weight%.

9. A method for forming a low dielectric constant boron nitride-containing thin film, comprising a process of forming a thin film on a substrate using a precursor for forming a low dielectric constant boron nitride-containing thin film according to claim 1.

10. In Paragraph 9, The process of forming a thin film on the above substrate is, A step of supplying the thin film forming precursor to the surface of a substrate; and A step comprising reacting the above-mentioned precursor for forming a thin film with a reactive gas; Method for forming a low dielectric constant boron nitride-containing thin film.

11. In Paragraph 10, A method for forming a low dielectric constant boron nitride-containing thin film, wherein the reactive gas comprises 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).

12. In Paragraph 10, A method for forming a low dielectric constant boron nitride-containing thin film, wherein the step of supplying the thin film forming precursor to the surface of the substrate is performed by vaporizing the low dielectric constant boron nitride-containing thin film forming precursor and transferring it into a reactor chamber to supply it.

13. In Paragraph 10, The step of reacting the above-mentioned precursor for forming a thin film with a reactive gas is: A method for forming a low dielectric constant boron nitride-containing thin film, which is performed under plasma application.

14. A low dielectric constant boron nitride-containing thin film manufactured by the method for forming a low dielectric constant boron nitride-containing thin film according to claim 9.

15. In Paragraph 14, The low dielectric constant boron nitride-containing thin film above is a thin film containing amorphous boron nitride.

16. In Paragraph 14, The low dielectric constant boron nitride-containing thin film is a low dielectric constant boron nitride-containing thin film having a dielectric constant of 1.5 to 4.

0.

17. In Paragraph 14, The above low dielectric constant boron nitride-containing thin film has a density of 1.5 g / cm³ calculated by X-ray reflectance measurement (XRR). 3 A low dielectric constant boron nitride-containing thin film that is the above.

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