KR20240060264A - Silicon precursor compound, Method of preparing the same, and Method for forming a thin film using the same - Google Patents

Abstract

The present invention provides a novel silicon precursor compound, a method for producing the same, and a method for forming a thin film using the precursor compound. The silicon precursor compound has a diazabutadiene ligand forming a double bond and a 5-membered ring structure, thereby producing a compound having a physicochemical stabilizing effect. In addition, the novel silicon precursor compound of the present invention contains a halogen group and is highly reactive, enabling rapid deposition on a substrate and forming a thin film with high purity.

Description

Silicon precursor compound, method of preparing the same, and method of forming a thin film using the precursor compound {Silicon precursor compound, Method of preparing the same, and Method for forming a thin film using the same}

The present invention relates to a silicon precursor compound, and more specifically, to a silicon precursor compound that can be used in the manufacture of semiconductor devices to form a thin film containing silicon, a manufacturing method thereof, and a thin film forming method using the precursor compound. .

Silicon-containing thin films are used in various fields such as semiconductors, solar cells, flat panel displays, and the aviation industry. In particular, in the semiconductor field, as semiconductor circuits become more highly integrated, the aspect ratio of semiconductor devices increases, and this leads to the important role of silicon-containing thin films that can be etched to selectively form layers such as diffusion barrier, insulating film, spacer, and anti-etch layer. It's getting worse. In addition, silicon-containing thin films can adjust their electrical properties depending on the type or amount of the constituent elements doped, and the thickness of the desired layer can be adjusted depending on the ligand that makes up the silicon precursor compound, making it suitable for use in various semiconductor device fields. It is being used.

A silicon-containing thin film can be formed by depositing a silicon precursor compound using atomic layer deposition (ALD) or chemical vapor deposition (CVD). In particular, silicon thin films deposited by ALD can improve device characteristics by improving thickness uniformity and physical properties, so the use of ALD has recently increased significantly. However, since CVD and ALD have different reaction mechanisms, there is a problem that a thin film of the desired quality cannot be produced by ALD using a silicon precursor compound suitable for conventional CVD.

Meanwhile, flat displays using OLED (organic light emitting diode) have superior characteristics than LCD (liquid crystal display) displays. The self-luminous characteristic of OLED does not require a backlight unit using LEDs, making it possible to produce an ultra-thin display. However, general OLEDs have the disadvantage of short lifespan because cathode oxidation and cathode delamination can occur due to moisture or oxygen.

Encapsulation is used as a method to protect and improve the lifespan of materials sensitive to moisture or oxygen, such as the OLED. A general method of encapsulating OLED is to use a metal can or glass lid, but it has the problem of being vulnerable to external shock and making it difficult to realize a flexible display. An encapsulation technology that has emerged recently is a thin-film encapsulation technology that protects OLEDs using organic or inorganic thin films. The thin film encapsulation technology is resistant to impact and does not use metal or glass, enabling lighter displays and lower manufacturing costs.

Thin film encapsulation technology is a technology that protects OLEDs by applying silicon oxide (SiO _x ), silicon nitride (SiN _x ), and aluminum oxide (Al _x O _y ) films. Among them _, SiO

Therefore, there is a need for the development of silicon precursor compounds that can form high-quality silicon-containing thin films at low temperatures through ALD.

Republic of Korea Patent No. 10-1308572 (2013.09.09.) Republic of Korea Patent No. 10-1569406 (2015.11.10.)

In order to solve the above-mentioned problems, the first object of the present invention is to provide a silicon precursor compound that has excellent thermal stability and can form a silicon-containing thin film with good film properties.

Additionally, the second object of the present invention is to provide a method for producing the silicon precursor compound of the first object.

Additionally, the third object of the present invention is to provide a method of forming a thin film of a semiconductor device using the silicon precursor compound of the first object.

In order to solve the first problem, the present invention provides a silicon precursor compound represented by the following formula (1).

[Formula 1]

.

(In the above formula, X is a halogen group selected from the group consisting of F, Cl and Br,

R ¹ and R ² are each independently hydrogen, C ₁ -C ₁₂ alkyl group, C ₃ -C ₁₂ alkylsilyl group,

R ³ and R ⁴ are each independently hydrogen, C ₁ -C ₁₂ alkyl group, halogen group, dialkylamine group (-NR ⁵ R ⁶ ) or alkylamine group (-NHR ⁷ ), and R ⁵ and R ⁷ are Each is independently a C ₁ -C ₄ alkyl group.)

In order to solve the second problem, the present invention provides N,N'-dialkylethane-1,2-diimine (dialkylethane) in which the hydrogen bonded to the nitrogen atom represented by Scheme 1 below is replaced with an alkali metal (M). Preparing -1,2-diimine); and

To prepare a compound by cyclizing N,N'-dialkylethane-1,2-diimine in which the hydrogen bonded to the nitrogen atom prepared by Scheme 1, represented by Scheme 2 below, is substituted with an alkali metal (M). It provides a method for producing a silicon precursor compound, including a step.

[Scheme 1]

[Scheme 2]

In order to solve the third problem, the present invention is to process the silicon precursor compound represented by Formula 1 by chemical vapor deposition (CVD), atomic layer deposition (ALD), and plasma enhanced chemical vapor deposition. A method of forming a silicon-containing thin film deposited by one or more methods selected from the group consisting of Chemical Vapor Deposition (PECVD) is provided.

The silicon precursor compound of the present invention is a compound that has excellent thermal stability due to a diamine ligand containing a double bond and high reactivity due to a halogen group. The silicon precursor compound has a fast deposition rate due to its high reactivity, making it possible to deposit a thin film with high purity. In addition, the compound exists in a liquid state at room temperature and pressure, making it easy to store and handle.

In addition, the method for producing a silicon precursor compound of the present invention can produce a compound having a physicochemical stabilizing effect by forming a 5-membered ring with the central metal Si in the diazabutadiene ligand.

In addition, the method for forming a silicon-containing thin film of the present invention is to process the silicon precursor compound through chemical vapor deposition (CVD), atomic layer deposition (ALD), and plasma enhanced chemical vapor deposition (PECVD). A silicon-containing thin film can be formed by deposition using one or more methods selected from the group consisting of. The thin film can be formed to a uniform and thin thickness even on surfaces with a high aspect ratio.

Figure 1 is a graph showing the results of 1H-NMR analysis of a silicon precursor compound ([ ⁱ Pr ₂ DAD] SiCl (DMA)) prepared according to an embodiment of the present invention. This is a graph showing the analysis results.
Figure 2 is a graph showing the results of thermogravimetric analysis (TGA) of a silicon precursor compound ([ ⁱ Pr ₂ DAD] SiCl (DMA)) prepared according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to embodiments and drawings so that those skilled in the art can easily implement the present invention. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art. Accordingly, the embodiments of the present invention may be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below and may also be embodied in other forms.

Throughout the specification of the present invention, when a part is said to “include” a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary.

Throughout the specification of the present invention, “a step of” or “a step of” does not mean a “step for.”

The term “precursor” used in the present invention refers to a substance at a stage before becoming a specific substance that can be finally obtained in a chemical reaction. The material at the previous stage refers not only to the material just one step before the synthesis of the material we want, but also to all materials in the series of processes for synthesizing the desired material. The specific substances include all substances such as metals, ions, proteins, nucleic acids, carbohydrates, and fats.

The term "thin film" used in the present invention refers to a very thin film of about 1 ㎛ or less formed on an insulated substrate such as glass, ceramic, or semiconductor using vacuum deposition or sputtering.

The term “deposition” used in the present invention is a term used in the semiconductor manufacturing process and refers to a method of heating and evaporating metal at high temperature and attaching the vapor to the surface of metal and non-metal in a thin film.

Example

The present invention provides a novel silicon precursor compound having the structure of Formula 1 below. The compound contains an azole having a double bond and a 5-membered ring structure and can be very stable physicochemically.

[Formula 1]

In the above formula, may be Cl. The halogen group can act as a good leaving group in the deposition process for thin film formation, increasing reactivity with water and increasing the surface adsorption rate, thereby increasing the growth rate of the thin film.

In the above formula, R ¹ to R ² may each independently be hydrogen, a C ₁ -C ₁₂ alkyl group, or a C ₃ -C ₁₂ alkylsilyl group, and may specifically be hydrogen or a C ₁ -C ₁₀ alkyl group, preferably hydrogen or It may be a C ₁ -C ₅ alkyl group, and more preferably a hydrogen or C ₁ -C ₂ alkyl group.

In the above formula, R ³ and R ⁴ may each independently be hydrogen, a C ₁ -C ₁₂ alkyl group, a halogen group, a dialkylamine group (-NR ⁵ R ⁶ ), or an alkylamine group (-NHR ⁷ ), and R ⁵ and R ⁷ may each independently be a C ₁ -C ₄ alkyl group. Specifically, in the above formula, R ³ and R ⁴ may each independently be hydrogen, C ₁ -C ₁₀ alkyl group, or halogen group, preferably hydrogen or C ₁ -C ₅ alkyl group, more preferably hydrogen or C ₁ -C ₂ It may be an alkyl group.

The silicon precursor compound may be a compound having the structure of Formula 2 below.

[Formula 2]

In the above formula, R ¹ to R ⁴ are the same as defined in Formula 1 above, so the above content is used.

The silicon precursor compound may be a compound having the structure of Formula 3 below.

[Formula 3]

In ^the above formula ^,

Additionally, the silicon precursor compound may be a compound having at least one structure among the following formulas 4 to 6.

[Formula 4]

[Formula 5]

[Formula 6]

The silicon precursor compound may be a compound having the structure of Formula 7 below.

[Formula 7]

In ^the above formula ^,

Additionally, the silicon precursor compound may be a compound having at least one structure among the following formulas 8 to 10.

[Formula 8]

[Formula 9]

[Formula 10]

Additionally, the silicon precursor compound may be a compound having at least one structure among the structures of Chemical Formula 11 below (Formulas 11-1 to 11-6).

[Formula 11]

In Formula 1, compounds having the structures of Formulas 3 to 11, wherein R ¹ to R ² are an isopropyl group or a tertbutyl group, can improve the bonding force of materials by pushing electrons to the central metal. Thermal stability may be increased due to the improved binding force. In addition, the compound may reduce the viscosity of the material by causing a steric hindrance effect, and the reduced viscosity may facilitate smooth transfer to the chamber. The novel silicon precursor compound exists in a liquid state in an environment at room temperature and pressure during storage and transportation, making storage and handling easy.

Additionally, the present invention provides a method for producing a novel silicon precursor compound having at least one structure of Formulas 1 to 11. The production method involves producing N,N'-dialkylethane-1,2-diimine in which the hydrogen bonded to the nitrogen atom is replaced with an alkali metal (M), as represented by Scheme 1 below. forming step; and

Forming N,N'-dialkylethane-1,2-diimine in which the hydrogen bonded to the nitrogen atom formed in Scheme 1, represented by Scheme 2 below, is substituted with an alkali metal (M) as a cyclized compound; Includes.

[Scheme 1]

[Scheme 2]

In Schemes 1 and 2, M may be an alkali metal, and specifically may be an alkali metal selected from the group consisting of lithium (Li), sodium (Na), and potassium (K). , preferably lithium. The alkali metal (M) may be added in excess to increase selectivity.

In Schemes ¹ and ² ,

N,N'-dialkyl ethane-1,2-diimine in which the hydrogen bonded to the nitrogen atom of Scheme 1 is substituted with an alkali metal (M) is N,N'-dialkyl ethane-1 in the first organic solvent. , It can be formed by reacting 2-diimine and an alkali metal. The first organic solvent may be one or more solvents selected from the group consisting of diethylether, tetrahydrofuran (THF), methylal, and dimethoxyethane (DME), Preferably it may be THF.

N,N'-dialkylethane-1,2-diimine in which the hydrogen bonded to the cyclized nitrogen atom of Scheme 2 is substituted with an alkali metal (M) is the nitrogen atom formed in Scheme 1 in the second organic solvent. It can be formed by reacting N,N'-dialkylethane-1,2-diimine in which the hydrogen bonded to is substituted with an alkali metal (M) and dihalodialkylsilane. The second organic solvent may be one or more solvents selected from the group consisting of hexane and toluene, and is preferably hexane.

Reaction Scheme 2 can be specifically expressed as Reaction Scheme 3 below, where X in Reaction Scheme 2 is Cl.

[Scheme 3]

The above production method can be produced at low temperature, specifically at 0°C to 40°C, and preferably at 0°C to 30°C.

In addition, the present invention uses a novel silicon precursor compound having at least one structure of Formulas 1 to 11, such as chemical vapor deposition (CVD), atomic layer deposition (ALD), and plasma chemistry. A method of forming a silicon-containing thin film using one or more methods selected from the group consisting of plasma enhanced chemical vapor deposition (PECVD) is provided. The precursor compound has excellent thermal stability and leaves almost no residue even at high temperatures, so it can form a high-quality thin film even in a high-temperature chemical vapor deposition process. The deposition can be done on a substrate.

The method of forming the silicon-containing thin film can be formed by additionally including a solvent in the precursor compound. The solvent may be included in 0% to 99% by weight of the total weight of the precursor compound, specifically 0% to 90% by weight, and preferably 0% to 80% by weight. The solvent may be one or more solvents selected from the group consisting of C ₅ to C ₁₀ nonpolar solvents, diethyl ether, dimethoxyethane, or THF polar solvents, and C ₆ to C ₁₀ aromatic solvents.

In the method of forming the silicon-containing thin film, the precursor compound may be uniformly mixed with an organic compound to prepare a composition for forming a silicon-containing thin film. The uniformly mixed means that the concentrations of the organometallic precursor compound and the organic compound are substantially the same throughout the entire region of the composition.

The organic compound may be one or more compounds selected from the group consisting of nonpolar organic compounds, aromatic organic compounds, and electron donor organic compounds. The nonpolar organic compound may be a C ₅ to C ₁₀ aliphatic hydrocarbon compound, and specifically may be a C ₅ to C ₁₀ linear, branched or cyclic alkane compound, preferably hexane or heptane. , octane, cyclohexane, neopentane, and mixtures thereof. The aromatic organic compound may be a C ₆ to C ₁₀ aromatic hydrocarbon compound, and preferably may be at least one mixture selected from the group consisting of benzene, toluene, xylene, and mixtures thereof. Examples of the electron donor organic compound include C ₂ to C ₁₂ alkylamine compounds, C ₃ to C ₁₂ alkyl allyl compounds, heterocyclic compounds containing oxygen and/or nitrogen, and C ₂ to C ₁₀ alkylamine compounds. It may be an ether compound or a mixture thereof, and specifically may be a C ₂ to C ₁₂ secondary or tertiary amine. The secondary amine may be dimethylamine, diethylamine, ethylmethylamine, and diisopropylamine, and the tertiary amine may be ethyldimethylamine, methyldiethylamine, triethylamine, tributyl imman, and tetramethylethylenediamine. You can.

The organic compound can improve the thermal stability and storage stability of the silicon precursor compound represented by Formula 1 to Formula 11 and reduce viscosity, and is vaporized during the deposition process so that the precursor compound can be deposited uniformly on the substrate. can do.

The organic compound may be mixed in an amount of 0.1 to 10 mol, specifically, 0.2 to 8 mol, and preferably 0.2 to 5 mol, based on 1 mole of the silicon precursor compound represented by Formula 1 to Formula 11. there is. If too little of the organic compound is mixed, the thermal stability of the precursor compound may be insufficient or the viscosity may not be sufficiently reduced, and if the organic compound is mixed excessively, the deposition time and energy of the precursor compound increase, resulting in reduced deposition efficiency. can do.

The precursor compound can grow a single atomic layer uniformly according to a self-limiting reaction by alternately supplying the elements necessary for thin film formation, so that a very thin thin film can be formed with the desired thickness and composition by atomic layer deposition. there is. The method of depositing the silicon precursor compound using the atomic layer deposition method specifically includes the following steps: i) transferring the silicon precursor compound to a chamber, ii) adsorbing the transferred compound onto a substrate to form the compound layer, iii) removing the non-adsorbed compound by injecting a first purge gas into the chamber, iv) forming a silicon oxide film by injecting a reaction gas into the chamber, and v) injecting a second purge gas into the chamber. The step of removing the remaining reaction gas and by-products can be repeated in one cycle to form a thin film. The repetition may specifically be 10 to 1,000 times, preferably 100 to 600 times. The first purge gas and the second purge gas may be an inert gas, specifically argon (Ar), nitrogen (N ₂ ), or helium (He) gas, and preferably argon gas.

The silicon-containing thin film is from the group consisting of a silicon film, a silicon low-k film, a silicon oxide film, a silicon nitride film, a silicon carbonitride film, and a silicon oxynitride film. It may be one or more deposited thin films of choice.

The method of forming the silicon-containing thin film can be formed by depositing the compound on a substrate at a temperature of 50 ℃ to 500 ℃, and specifically, can be formed by depositing the compound on a substrate at a temperature of 50 ℃ to 500 ℃, preferably Can be formed by depositing on a substrate at a temperature of 50 ℃ to 500 ℃. In addition, the method of forming the silicon-containing thin film can be formed by depositing the compound on a substrate in a reactor in which the internal pressure is maintained at 0.2 torr to 10 torr, preferably in a reactor maintained at 0.2 torr to 8 torr. It can be formed by depositing the compound on a substrate.

The method of forming the silicon-containing thin film may be preceded by transferring the novel silicon precursor compound onto a substrate before deposition, if necessary for the process. The transport of the compound can be carried out using bubbling method, vapor phase MFC (Mass Flow controller), Direct Gas Injection (DGI), Direct Liquid Injection (DLI), and organic The metal precursor composition may be transported by one or more methods selected from the group consisting of an organic solution supply method in which the metal precursor composition is dissolved in an appropriate organic solvent and transported.

The bubbling method or direct gas injection method can move the compound to the top of the substrate along with an appropriate carrier gas. As the moving gas, any gas that does not react with the compound can be used without limitation, and specifically, a gas composed of argon (Ar), nitrogen (N ₂ ), helium (He), hydrogen (H ₂ ), and combinations thereof. can be used.

The organic solution supply method can use ethylbenzene, mesitylene, decane, or dodecane to move the compound to the top of the substrate.

The method of forming the silicon-containing thin film can be performed by supplying a reaction gas together with the silicon precursor compound. The reaction gas is a gas contained in an oxygen source or nitrogen source, silane (SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , etc.), alkyl silane (SiH ₂ Me ₂ , SiH ₂ Et ₂ , etc.), amino silane (N (SiH ₃ ) ₃ ) and mixtures thereof.

Hereinafter, the present invention can be explained in detail through manufacturing examples and experimental examples.

Prerequisites for the experiment

In the present invention, the standard pore line (Schlenk technique) was used as a technique for synthesizing the silicon precursor compound, and the synthesis of all materials was performed under a nitrogen atmosphere. N,N`-diisopropylethane-1,2-diimine ( ⁱ Pr ₂ DAD), dimethylamino trichlorosilane ( dimethylamino trichlorosilane, ethylmethylamino trichlorosilane, diethylamino trichlorosilane, tetrahydrofuran, hexane, lithium and benzene-d ₆ d ₆ , C ₆ D ₆ ) were purchased and used from Aldrich. In addition, the solvents tetrahydrofuran, hexane, and benzene-d ₆ were stirred with CaH ₂ for a day to completely remove residual moisture before use, and then fractionated and purified.

<Manufacturing Example 1> [ ⁱ Pr ₂ Preparation of DAD]SiCl(DMA)

29.5 g (0.21 mmol) of N,N`-diisopropylethane-1,2-diimine was added to a 500 ml flask containing 250 ml of tetrahydrofuran. diimine, ⁱ Pr ₂ DAD) was added and dissolved while stirring at 0°C. After dissolution, 3.2 g (0.46 mol) of lithium was added to the solution and stirred at room temperature for 24 hours to prepare a compound of formula 12 below.

[Formula 12]

30 g (0.16 mol) of dimethylamino trichlorosilane was added to a different 1 liter flask and diluted with 100 ml of hexane. The compound of Formula 12 was slowly added to the diluted solution and stirred at room temperature for 12 hours. After stirring, the mixed solution was filtered to obtain an orange solution and the solvent was removed by reducing the pressure. The orange solution from which the solvent was removed was distilled under reduced pressure to obtain [ ⁱ Pr ₂ DAD] SiCl (DMA), a colorless compound of Chemical Formula 11-1 without viscosity.

[Formula 11-1]

Yield: 23.0 g (55.0%)

Boiling point (b.p): 50℃ at 0.4 torr.

Referring to Figure 1, the compound of Chemical Formula 11-1 prepared in <Preparation Example 1> was manufactured at 400 Mhz. ¹ The results of H-NMR (JEOL JNM-ECS 400 Hz NMR spectrometer) analysis were confirmed.

¹ H-NMR(C ₆ D ₆ ): δ 1.13 (-NHC(C H ₃ ) ₂ , sep, 12H),

δ 2.49 (Si(N(C H ₃ ) ₂ , s, 6H),

δ 3.28 (-N H C(CH ₃ ) ₂ , quar, 2H),

δ 5.63 (-NC H = H CN-, s, 2H).

Through the ¹ H-NMR analysis results, the chemical shift (δ) of the sample compared to the reference material can be confirmed. Specifically, the structural difference can be confirmed by measuring the resonance absorption line of the reference material and the sample, and measuring how much the position of the resonance absorption line of the sample differs from the position of the resonance absorption line of the reference material. A representative reference material is tetramethyl silane. The chemical shift is recorded in PPM units and means the ratio of the frequency (Hz) shifted from the resonance absorption line of tetramethyl silane, a reference material, to the overall device frequency (Hz), and can be expressed as δ (delta scale).

<Manufacturing Example 2> [ ⁱ Pr ₂ Preparation of DAD]SiCl(EMA)

A silicon precursor compound was prepared in the same manner as <Preparation Example 1> except that ethylmethylamino trichlorosilane rather than dimethylamino trichlorosilane was used. As a result, [ ⁱ Pr ₂ DAD] SiCl (EMA), a colorless compound of Chemical Formula 11-2 without viscosity, was obtained.

[Formula 11-2]

Yield: 13.8 g (30.0%)

Boiling point (b.p): 56℃ at 0.47 torr.

¹ H-NMR(C ₆ D ₆ ): δ 0.97 (Si(N(CH ₃ )(CH ₂ C H ₃ )), t, 3H),

δ 1.17 (-NHC(C H ₃ ) ₂ , t, 12H),

δ 2.5 (Si(N(C H ₃ )(CH ₂ CH ₃ )), s, 3H),

δ 2.93 (Si(N(CH ₃ )(C H ₂ CH ₃ )), q, 2H),

δ 3.33 (-N H C(CH ₃ ) ₂ , sep, 2H),

δ 5.66 (-NC H = H CN-, s, 2H).

<Production Example 3> [ ⁱ Pr ₂ Preparation of DAD]SiCl(DEA)

A silicon precursor compound was prepared in the same manner as <Preparation Example 1> except that diethylamino trichlorosilane rather than dimethylamino trichlorosilane was used. As a result, [ ⁱ Pr ₂ DAD] SiCl (DMA), a colorless compound of Chemical Formula 11-3 without viscosity, was obtained.

[Formula 11-3]

Yield: 28.6 g (58.0%)

Boiling point (b.p): 64℃ at 0.39 torr.

¹ H-NMR(C ₆ D ₆ ): δ 0.98 (Si(N(CH ₂ C H ₃ ) ₂ ), t, 6H),

δ 1.18 (-NHC(C H 3)2, t, 12H),

δ 2.95 (Si(N(C H ₂ CH ₃ ) ₂ ),q, 4H),

δ 3.37 (-N H C(CH ₃ ) ₂ , sep, 2H),

δ 5.68 (-NC H = H CN-, s, 2H).

<Production Example 4> [ ^t Bu ₂ Preparation of DAD]SiCl(DMA)

59.7 g (0.35 mmol) of N,N`-ditertbutylethane-1,2-diimine was added to a 500 ml flask containing 350 ml of tetrahydrofuran. diimine, ^tBu ₂ DAD) was added and dissolved while stirring at 0°C. After dissolution, 5.4 g (0.78 mol) of lithium was added to the solution and stirred at room temperature for 24 hours to prepare a compound of Formula 13 below.

[Formula 13]

57 g (0.31 mol) of dimethylamino trichlorosilane was added to a different 1 liter flask and diluted with 100 ml of hexane. The compound of Formula 13 was slowly added to the diluted solution and stirred at room temperature for 12 hours. After stirring, the mixed solution was filtered to obtain an orange solution and the solvent was removed by reducing the pressure. The orange solution from which the solvent was removed was distilled under reduced pressure to obtain [ ^t Bu ₂ DAD] SiCl (DMA), a non-viscous, light yellow compound of Chemical Formula 11-4.

[Formula 11-4]

Yield: 41.6 g (47.0%)

Boiling point (b.p): 58℃ at 0.4 torr.

¹ H-NMR(C ₆ D ₆ ): δ 1.24 (-NC(CH ₃ ) ₃ , s, 18H),

δ 2.44 (Si(N(CH ₃ ) ₂ , s, 6H),

δ 5.77 (-NCH=HCN-, s, 2H).

<Production Example 5> [ ^t Bu ₂ Preparation of DAD]SiCl(EMA)

A silicon precursor compound was prepared in the same manner as <Preparation Example 4> except that ethylmethylamino trichlorosilane rather than dimethylamino trichlorosilane was used. As a result, 35.1 g of [ ^tBu ₂ DAD]SiCl(EMA), a non-viscous, light yellow compound of Chemical Formula 11-5, was obtained (yield 56%).

[Formula 11-5]

Yield: 35.1 g (56.0%)

Boiling point (b.p): 72 ℃ at 0.42 torr,

¹ H-NMR(C ₆ D ₆ ): δ 0.95 (Si(N(CH ₃ )(CH ₂ C H ₃ )), t, 3H),

δ 1.26 (-NC(C H ₃ ) ₃ , s, 18H),

δ 2.44 (Si(N(C H ₃ )(CH ₂ CH ₃ )), s, 3H),

δ 2.89 (Si(N(CH ₃ )(C H ₂ CH ₃ )), q, 2H),

δ 5.77 (-NC H = H CN-, s, 2H).

<Production Example 6> [ ^t Bu ₂ Preparation of DAD]SiCl(DEA)

A silicon precursor compound was prepared in the same manner as <Preparation Example 4> except that diethylamino trichlorosilane rather than dimethylamino trichlorosilane was used. As a result, [ ^t Bu ₂ DAD] SiCl (DEA), a non-viscous, light yellow compound of Chemical Formula 11-6, was obtained.

[Formula 11-6]

Yield: 43.5 g (66.0%)

Boiling point (b.p): 76℃ at 0.3 torr.

¹ H-NMR(C ₆ D ₆ ): δ 0.98 (Si(N(CH2 _C H ₃ ) ₂ ), t, 6H),

δ 1.29 (-NC(C H ₀ ) ₃ , s, 18H),

δ 2.96 (Si(N(C H ₂ CH ₃ ) ₂ ), q, 4H),

δ 5.77 (-NC H = H CN-, s, 2H).

<Experimental Example 1> Thermal analysis of silicon precursor compound

In order to confirm the thermal properties (thermal stability and decomposition temperature) of the compound of Formula 12 prepared in Preparation Example 4, the thermal decomposition temperature was confirmed using TA-Q 600, a thermogravimetric analysis (TGA).

Specifically, argon (Ar) with a flow rate of 100 cc/min was used as the transport gas, and 10 mg of the formula 11-1 was added to a thermogravimetric analyzer in the temperature range of 30 ℃ to 500 ℃ with a temperature increase rate of 10 ℃/min. The compound was added and weight loss due to thermal decomposition temperature was measured. Figure 2 shows the results of TGA analysis.

Referring to Figure 2, as a result of analyzing the compound of Chemical Formula 11-1 prepared in <Preparation Example 1> using a thermogravimetric analyzer, it was confirmed that the temperature at which the mass of the compound decomposes to 50% was 185°C. Therefore, it was confirmed that the compound had excellent thermal stability and that a thin film could be deposited and formed in a high temperature deposition process. Meanwhile, as a result of checking the remaining residue after raising the temperature of the TGA to 500° C., it was confirmed that almost no residue existed even at high temperatures.

In conclusion, the silicon precursor compound of the present invention has excellent thermal stability, is easy to store due to small residues, and can form a silicon-containing thin film with good film properties by depositing the compound at high temperature.

Claims (15)

A silicon precursor compound represented by the following formula (1).
[Formula 1]

(In the above formula, X is a halogen group selected from the group consisting of F, Cl and Br,
R ¹ and R ² are each independently hydrogen, a C ₁ -C ₁₂ alkyl group, or a C ₃ -C ₁₂ alkylsilyl group,
R ³ and R ⁴ are each independently hydrogen, C ₁ -C ₁₂ alkyl group, halogen group, dialkylamine group (-NR ⁵ R ⁶ ) or alkylamine group (-NHR ⁷ ), and R ⁵ and R ⁷ are Each is independently a C ₁ -C ₄ alkyl group.) According to paragraph 1,
Among the silicon precursor compounds represented by Formula 1, X is Cl. According to paragraph 1,
Among the silicon precursor compounds represented by Formula 1, R ¹ to R ² are isopropyl groups. According to paragraph 3,
The silicon precursor compound is represented by at least one of the following formulas 4 to 6.
[Formula 4]

[Formula 5]

[Formula 6]

(In the above formula, X is a halogen group selected from the group consisting of F, Cl and Br.) According to paragraph 1,
Among the silicon precursor compounds represented by Formula 1, R ¹ to R ² are tert-butyl groups. According to clause 5,
The silicon precursor compound is represented by at least one of the following formulas 8 to 10.
[Formula 8]
,
[Formula 9]

[Formula 10]

(In the above formula, X is a halogen group selected from the group consisting of F, Cl and Br.) Forming N,N'-dialkylethane-1,2-diimine in which the hydrogen bonded to the nitrogen atom is substituted with an alkali metal (M), represented by Scheme 1 below; and
Forming N,N'-dialkylethane-1,2-diimine in which the hydrogen bonded to the nitrogen atom formed in Scheme 1, represented by Scheme 2 below, is substituted with an alkali metal (M) as a cyclized compound; Method for producing a silicon precursor compound comprising.
[Scheme 1]

[Scheme 2]

(In Scheme 1 to Scheme 2, M is an alkali metal,
X is a halogen group selected from the group consisting of F, Cl and Br,
R ¹ and R ² are each independently hydrogen, C ₁ -C ₁₂ alkyl group, C ₃ -C ₁₂ alkylsilyl group,
R ³ and R ⁴ are each independently hydrogen, C ₁ -C ₁₂ alkyl group, halogen group, dialkylamine group (-NR ⁵ R ⁶ ) or alkylamine group (-NHR ⁷ ), and R ⁵ and R ⁷ are Each is independently a C ₁ -C ₄ alkyl group.) In clause 7,
N,N'-dialkylethane-1,2-diimine, in which the hydrogen bonded to the nitrogen atom is substituted with an alkali metal (M), is N,N' in the first organic solvent. -A method for producing a silicon precursor compound formed by reacting dialkylethane-1,2-diimine and an alkali metal. In clause 7,
The cyclized compound is N,N'-dialkyl ethane-1,2-diimine and dihalodialkylsilane in which the hydrogen bonded to the nitrogen atom is substituted with an alkali metal (M) in the second organic solvent. ), a manufacturing method formed by reacting. According to clause 8,
The first organic solvent is one or more solvents selected from the group consisting of diethylether, tetrahydrofuran (THF), methylal, and dimethoxyethane (DME). . According to clause 9,
The production method wherein the second organic solvent is one or more solvents selected from the group consisting of hexane and toluene. In clause 7,
A manufacturing method wherein the silicon precursor compound is manufactured at a temperature of 0 ℃ to 40 ℃. Chemical vapor deposition (CVD), atomic layer deposition (ALD), and plasma enhanced chemical vapor deposition using the silicon precursor compound according to any one of claims 1 to 6. , PECVD) A method of forming a silicon-containing thin film by one or more methods selected from the group consisting of According to clause 13,
The silicon-containing thin film is from the group consisting of a silicon film, a silicon low-k film, a silicon oxide film, a silicon nitride film, a silicon carbonitride film, and a silicon oxynitride film. A method of forming a silicon-containing thin film, wherein one or more deposited thin films are selected. According to clause 13,
A method of forming a silicon-containing thin film, wherein the deposition is deposited at a temperature of 50 ℃ to 500 ℃ in a reactor with an internal pressure of 2 torr to 10 torr.