KR20240080329A - Precursor comprising for yttrium or actinoid containg thin film, deposition method of film and semiconductor device of the same - Google Patents

Abstract

The present invention provides a precursor for forming a yttrium (Y) or scandium (Sc)-containing thin film, characterized in that it contains a compound represented by Formula 1, a method for forming a yttrium or scandium-containing thin film using the same, and a yttrium or scandium-containing thin film comprising the yttrium or scandium-containing thin film. Regarding semiconductor devices, the precursor for forming a thin film has a chemical structure containing an asymmetric cyclopentadienyl ligand and an asymmetric amidinate ligand, thereby exhibiting characteristics of high heat resistance and high volatility, through which a high-quality thin film can be formed. It shows the effect.

Description

A precursor for forming a thin film containing yttrium or scandium, a method of forming a thin film containing yttrium or scandium using the same, and a semiconductor device including the thin film containing yttrium or scandium. {PRECURSOR COMPRISING FOR YTTRIUM OR ACTINOID CONTAING THIN FILM, DEPOSITION METHOD OF FILM AND SEMICONDUCTOR DEVICE OF THE SAME}

The present invention relates to a precursor for forming a thin film containing yttrium (Y) or scandium (Sc), a method of forming a thin film containing yttrium or scandium using the same, and a semiconductor device including the thin film containing yttrium or scandium, and more specifically, to an asymmetric cycle. A precursor for forming thin films containing yttrium or scandium, which provides a precursor with high heat resistance and high volatility through a chemical structure containing a pentadienyl ligand and an asymmetric amidinate ligand, and can form a high-quality thin film through this, and a thin film using the same It relates to a forming method and a semiconductor device including the thin film.

Due to the improvement in integration through the miniaturization of the line width of semiconductor devices, the space allowed for the implementation of capacitor structures is limited in terms of line width, and there are limitations in the manufacturing method of semiconductor devices for implementing capacitor structures using existing silicon-based dielectrics. In addition, as high dielectric thin films are applied to replace silicon-based dielectrics, a problem arises in which leakage current due to the band gap is significantly deteriorated.

As one of the ways to solve this problem, a technology to increase crystallization characteristics by forming a thin film in a high temperature process is required, and for this, it is necessary to optimize the precursor used to form the thin film.

As an example of a method for optimizing the precursor used to form a conventional thin film, various doping precursors that can improve dielectric constant and leakage current characteristics can be proposed. However, most of these precursors have low thermal stability or low volatility characteristics. Therefore, in order to optimize the precursor for thin film formation, improving the physical properties of the precursor, such as high heat resistance and high volatility, is a very important task.

The present invention was conceived in consideration of the above prior art, and its purpose is to provide a novel yttrium- or scandium-containing precursor for forming thin films that can exhibit chemical properties suitable as a precursor for forming thin films.

In addition, the purpose is to provide a precursor for forming a thin film containing yttrium or scandium, which exhibits chemical properties of high heat resistance and high volatility, and is in a liquid state at room temperature, a solid state with a low melting point, or a solid state with high solubility in a solvent. do.

Additionally, the purpose is to provide a method of forming a thin film using the precursor.

Additionally, the object is to provide a semiconductor device including the thin film.

The precursor for forming a thin film of the present invention to solve the above problems is characterized by containing a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

M is yttrium (Y) or scandium (Sc), and R ₁ to R ₈ are each independently a hydrogen atom, or a C ₁ -C ₆ straight-chain, branched or cyclic alkyl group, alkenyl group, alkoxy group, or amine group. Or it is a silyl group.

At this time, in Formula 1, R ₆ and R ₈ may be different C ₁ -C ₆ straight-chain, branched, or cyclic alkyl groups.

Additionally, in Formula 1, two or more of R ₁ to R ₅ may be different C ₁ -C ₆ straight-chain, branched, or cyclic alkyl groups.

In addition, in Formula 1, R ₆ and R ₈ are different C ₁ -C ₆ straight-chain, branched or cyclic alkyl groups, or at least two of R ₁ to R ₅ are different C ₁ -C ₆ alkyl groups. It may be a straight-chain, branched, or cyclic alkyl group.

Additionally, in Formula 1, one or more of R ₁ to R ₅ may be an ethyl group (Et) or a methyl group (Me).

Additionally, in Formula 1, one or more of R ₆ and R ₈ may be a C ₁ -C ₆ branched alkyl group.

In addition, in Formula 1, any one or more of R ₆ and R ₈ is a t-butyl group (t-Bu), s-butyl group (sec-Bu), isobutyl group (i-Bu), or isopropyl group. (iPr), or t-amyl group.

Additionally, in Formula 1, one of R ₆ and R ₈ may be a t-butyl group and the other may be an isopropyl group.

In addition, in Formula 1, R ₇ is an ethyl group (Et), n-propyl group (n-Pr), n-butyl group (n-Bu), isopropyl group (i-Pr), s-butyl group (sec- Bu) or isobutyl group (i-Bu).

In addition, the thin film forming method of the present invention is characterized by including a process of forming a thin film on a substrate using the thin film forming precursor.

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 the thin film forming precursor on the surface of the substrate, and a process of reacting the precursor thin film with a reactive gas.

In addition, the reactive gases include nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (N ₂ H ₄ ), nitrous oxide (N ₂ O), oxygen (O ₂ ), water vapor (H ₂ O), and ozone (O). ₃ ), one or more of hydrogen peroxide (H ₂ O ₂ ), silane, hydrogen (H ₂ ), and diborane (B ₂ H ₆ ) can be used.

Additionally, the process of forming the precursor thin film may include vaporizing the thin film forming precursor and transferring it into the chamber.

In addition, the deposition is a spin-on dielectric (SOD) process, a low temperature plasma (LTP) process, a chemical vapor deposition (CVD) process, and a plasma enhanced chemical vapor deposition (CVD) process. PECVD) process, High Density Plasma -Chemical Vapor Deposition (HDPCVD) process, Atomic Layer Deposition (ALD) process, or Plasma-Enhanced Atomic Layer Deposition (PEALD) process. It can be performed by any one of the following.

Additionally, the process of forming a thin film on the substrate may include supplying the thin film forming precursor to the substrate and applying plasma to form the thin film.

Additionally, the semiconductor device of the present invention is characterized by including a thin film manufactured by the above thin film forming method.

The precursor for forming a yttrium- or scandium-containing thin film according to the present invention contains an asymmetric cyclopentadienyl and an asymmetric amidinate ligand, so the precursor compound has excellent structural stability and exhibits high volatility and high heat resistance characteristics, thereby forming a yttrium- or scandium-containing thin film. It shows an effect suitable for use in the forming process.

In addition, a high-quality yttrium- or scandium-containing thin film can be formed using the thin film forming precursor, and a semiconductor device including a yttrium- or scandium-containing thin film manufactured by the thin film forming method can be provided.

Figure 1 shows the ¹ H NMR analysis results of bis(ethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
Figure 2 shows the TGA analysis results of bis(ethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
Figure 3 shows the DSC analysis results of bis(ethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
Figure 4 shows the ¹ H NMR analysis results of bis(ethylcyclopentadienyl)(isopropyl-t-butyl-ethylamidinato)yttrium.
Figure 5 shows the ¹ H NMR analysis results of bis(diethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
Figure 6 shows the TGA analysis results of bis(diethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
Figure 7 shows the DSC analysis results of bis(diethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
Figure 8 shows the ¹ H NMR analysis results of bis(ethylmethylcyclopentadienyl)(diisopropyl-methylamidinato)yttrium.

Hereinafter, the present invention will be described in more detail. Terms or words used in this specification and claims should not be construed as limited to their common or dictionary meanings, and the inventor may appropriately define the concept of terms in order to explain his or her invention in the best way. It must be interpreted with meaning and concept consistent with the technical idea of the present invention based on the principle that it is.

The precursor for forming a thin film according to the present invention is for forming a thin film containing yttrium or scandium, and is characterized by containing a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

M is yttrium (Y) or scandium (Sc), and R ₁ to R ₈ are each independently a hydrogen atom, or a C ₁ -C ₆ straight-chain, branched or cyclic alkyl group, alkenyl group, alkoxy group, or amine group. Or it is a silyl group.

The precursor for forming the thin film can form various types of compounds depending on the type of functional group.

In one embodiment of the compound represented by Formula 1, R ₆ and R ₈ may be different C ₁ -C ₆ straight-chain, branched, or cyclic alkyl groups. In this chemical structure, an asymmetric structure can be formed by different forms of R ₆ and R ₈ .

Additionally, in Formula 1, two or more of R ₁ to R ₅ may be different C ₁ -C ₆ straight-chain, branched, or cyclic alkyl groups, thereby forming an asymmetric structure.

In addition, in Formula 1, R ₆ and R ₈ are different C ₁ -C ₆ straight-chain, branched or cyclic alkyl groups, or at least two of R ₁ to R ₅ are different C ₁ -C ₆ alkyl groups. It may be a straight-chain, branched, or cyclic alkyl group, which can increase the overall structural asymmetry of the compound.

Additionally, in Formula 1, any one or more of R ₁ to R ₅ may be an ethyl group (Et) or a methyl group (Me), and one or more of R ₆ and R ₈ may be a C ₁ -C ₆ group. It may be a functional alkyl group, and one or more of R ₆ and R ₈ is a t-butyl group (t-Bu), s-butyl group (sec-Bu), isobutyl group (i-Bu), or isopropyl group. (iPr), or it may be a t-amyl group. In addition, one of R ₆ and R ₈ may be a t-butyl group and the other may be an isopropyl group, and R ₇ may be an ethyl group (Et), an n-propyl group (n-Pr), or an n-butyl group (n- Bu), isopropyl group (i-Pr), s-butyl group (sec-Bu), or isobutyl group (i-Bu).

This chemical structure was found to be suitable for forming a high-quality thin film because it has excellent structural stability and exhibits high volatility and high heat resistance properties.

In addition, the thin film forming precursor of the present invention may additionally include a solvent for dissolving or diluting the precursor compound in consideration of the conditions and efficiency of the thin film forming process. The solvent may be any one of C ₁ -C ₁₆ saturated or unsaturated hydrocarbons, ketones, ethers, glymes, esters, tetrahydrofuran, tertiary amines, or mixtures thereof. Examples of the C ₁ -C ₁₆ saturated or unsaturated hydrocarbon include toluene and heptane, and examples of the tertiary amine include dimethylethylamine.

In particular, depending on the chemical structure, the precursor compound for forming a thin film may be in a solid state at room temperature. In this case, the compound can be dissolved by including the solvent. That is, when the solvent is included, it is contained in a solvent and amount capable of dissolving the precursor compound, and is preferably contained in 1 to 99% by weight based on the total weight of the precursor for forming the thin film.

A thin film is formed on a substrate using a precursor for forming a thin film containing or not containing the solvent. Specifically, the process of forming a thin film on a substrate may include a process of forming a precursor thin film by depositing the thin film forming precursor on the surface of the substrate, and a process of reacting the precursor thin film with a reactive gas.

At this time, the reactive gas is nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (N ₂ H ₄ ), nitrous oxide (N ₂ O), oxygen (O ₂ ), water vapor (H ₂ O), and ozone (O). ₃ ), one or more of hydrogen peroxide (H ₂ O ₂ ), silane, hydrogen (H ₂ ), and diborane (B ₂ H ₆ ) can be used.

Depending on the type of the reactive gas, various types of thin films, such as yttrium or scandium metal thin films, oxide, nitride, and oxynitride thin films, can be formed.

Additionally, the process of forming the precursor thin film may include a process of vaporizing the thin film forming precursor and transferring it into the chamber. For this purpose, a precursor containing a solvent may be used as described above. Additionally, if it exists in a liquid state at room temperature and can be vaporized, the thin film forming precursor can be transported into the chamber without a separate solvent.

In addition, the deposition is a spin-on dielectric (SOD) process, a low temperature plasma (LTP) process, a chemical vapor deposition (CVD) process, and a plasma enhanced chemical vapor deposition (CVD) process. PECVD) process, High Density Plasma -Chemical Vapor Deposition (HDP-CVD) process, Atomic Layer Deposition (ALD) process, or Plasma-Enhanced Atomic Layer Deposition (PEALD) ) can be performed by any one of the processes. For example, when applying the HDP-CVD process, the high vacuum and high Because it can be carried out at high power, it is possible to form a thin film that is structurally dense and has excellent mechanical properties.

Additionally, the process of forming a thin film on a substrate may include forming a thin film of a metal, oxide, nitride, oxynitride, etc. by supplying the thin film forming precursor to the substrate and applying plasma in the presence of a reactant.

Additionally, the process of forming the thin film can be performed under chamber pressure conditions of 1 to 1000 mTorr. In addition, the source power for forming plasma in the chamber is 500 to 9,000 W, and the bias power is 0 to 5,000 W. Additionally, the bias power may not be applied depending on the case.

Additionally, the process of forming a thin film on the substrate may be performed at a temperature range of 150 to 500°C.

Additionally, when supplying the thin film forming precursor, a second metal precursor may be introduced as needed to further improve the electrical properties, that is, capacitance or leakage current value, of the final formed metal film. The second metal precursor is silicon (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb), barium (Ba), hafnium (Hf), tantalum (Ta), and actinium (Ac). ) A metal precursor containing one or more metals (M") selected from atoms may be optionally further supplied. The second metal precursor may be an alkylamide-based compound or an alkoxy-based compound containing the metal. For example, When the metal is Si, the second metal precursor is SiH(N(CH ₃ ) ₂ ) ₃ , Si(N(C ₂ H ₅ ) ₂ ) ₄ , Si(N(C ₂ H ₅ )(CH ₃ )) ₄ , Si(N(CH ₃ ) ₂ ) ₄ , Si(OC ₄ H ₉ ) ₄ , Si(OC ₂ H ₅ ) ₄ , Si(OCH ₃ ) ₄ , Si(OC(CH ₃ ) ₃ ) ₄ , etc. can be used. You can.

The supply of the second metal precursor may be carried out in the same manner as the supply method of the thin film formation precursor, and the second metal precursor may be supplied together with the precursor onto the thin film formation substrate, or the supply of the precursor may be completed. It may then be supplied sequentially.

The precursor for forming the thin film and optionally the second metal precursor as described above are preferably maintained at a temperature of 50 to 250° C. before being supplied into the reaction chamber for contact with the substrate for forming the thin film, more preferably 100 to 200° C. It is recommended to maintain a temperature of ℃.

In addition, after supplying the precursor and prior to supplying the reactive gas, it assists the movement of the precursor and optionally the second metal precursor onto the substrate, ensures an appropriate pressure for deposition within the reactor, and also helps remove impurities present in the chamber, etc. In order to release it to the outside, a process of purging an inert gas such as argon (Ar), nitrogen (N ₂ ), or helium (He) may be performed in the reactor. At this time, it is preferable that the inert gas is spread so that the pressure inside the reactor is 1 to 5 Torr.

Additionally, in addition to plasma treatment, a heat treatment or light irradiation treatment process may be performed to provide heat energy for deposition of a thin film forming precursor, and may be performed according to a conventional method. Preferably, in order to produce a thin film having the desired physical state and composition at a sufficient growth rate, the treatment process is preferably performed so that the temperature of the substrate in the reactor is 100 to 1,000°C, preferably 250 to 400°C. .

In addition, during the treatment process, as described above, argon is used in the reactor to help the reactant move onto the substrate, to maintain an appropriate pressure for deposition within the reactor, and to release impurities or by-products present in the reactor to the outside. A process of purging an inert gas such as (Ar), nitrogen (N ₂ ), or helium (He) may be performed.

The above process of adding the precursor for forming a thin film, adding the reactant, and adding the inert gas is one cycle. A thin film can be formed by repeating the process one or more cycles.

Additionally, thin films manufactured by applying the thin film forming process can be used in various semiconductor devices.

Hereinafter, the effects of the present invention will be explained through examples.

[Synthesis Example 1] Bis(ethylcyclopentadienyl)yttrium chloride [(EtCp) ₂ Synthesis of [YCl]

To a solution of 300 ml of THF and 48.22 g (0.512 mol) of ethylcyclopentadiene, 204.9 ml (0.512 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise at -78°C, stirred for 30 minutes, and then heated to room temperature. , and further stirred for 2 hours to prepare a Li-EtCp solution. 50.0 g (0.256 mol) of yttrium chloride and 150 ml of toluene were added to a new flask, and then cooled to -78°C while stirring. The previously prepared Li-EtCp solution was slowly added dropwise to the flask containing the yttrium chloride mixture, stirred at -78°C for 30 minutes, then raised to room temperature and stirred for 12 hours to synthesize bis(ethylcyclopentadienyl)yttrium chloride. did.

[Synthesis Example 2] Bis(ethylcyclopentadienyl)(isopropyl-tertiary butyl-methylamidinato)yttrium [(EtCp) ₂ Y( ⁱ Pr ^t Synthesis of [BuMe-AMD)]

Add 40.02 g (0.256 mol) of isopropyl-t-butyl-methylamidinate to 300 ml of THF, cool to -78°C, and then slowly add 102.4 ml (0.256 mol) of n-BuLi hexane solution (2.5 M) dropwise. Li-( ⁱ Pr ^t BuMe-AMD) was prepared. The solution was stirred at -78°C for 30 minutes, then warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-( ⁱ Pr ^t BuMe-AMD) solution was slowly added dropwise to a flask containing (EtCp) ₂ YCl at room temperature and stirred at room temperature for 12 hours. The mixture was evaporated under vacuum, dissolved in 250 ml of pentane, filtered, and the solvent and volatile substances were evaporated under vacuum. The resulting red liquid was obtained as a light yellow solid at 250°C and 32mTorr. The yield was 55.4g (50.3%). The NMR (AV400MHz HD, Bruker company) analysis results are shown in Figure 1, and the characteristic peaks are as follows.

¹ H NMR (C ₆ D ₆ , 25°C): 0.97(d, 6H), 1.10(s, 9H), 1.25(t, 3H), 1.63(s, 3H), 2.54(q, 4H), 3.28( m, 1H), 6.08(dt, 8H).

The light yellow solid left almost no residual mass at 1% during TGA (SDT Q600 from TA Instruments) analysis, which was measured at a temperature rise rate of 10°C/min in an atmosphere flowing nitrogen at 200 mL/min. These results are shown in Figure 2. The TGA analysis results showing the percentage of weight loss according to temperature change are shown in Figure 2.

The light yellow solid sample was placed in an airtight container for DSC and maintained at 40°C for 10 minutes, and then a decomposition peak was observed at 439°C during DSC (Discovery 25, TA instrument) analysis measured at a temperature rise rate of 10°C/min. . These results are shown in Figure 3. The DSC analysis results showing the change in thermal energy according to temperature change are shown in Figure 3.

[Synthesis Example 3] Bis(ethylcyclopentadienyl)(isopropyl-tertiary butyl-ethylamidinato)yttrium [(EtCp) ₂ Y( ⁱ Pr ^t Synthesis of [BuEt-AMD)]

Add 43.61 g (0.256 mol) of isopropyl-tertiary butyl-ethylamidinate to 300 ml of THF, cool to -78°C, and then slowly add 102.4 ml (0.256 mol) of n-BuLi hexane solution (2.5 M) dropwise. Li-( ⁱ Pr ^t BuEt-AMD) was prepared. The solution was stirred at -78°C for 30 minutes, then warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-( ⁱ Pr ^t BuEt-AMD) solution was slowly added dropwise to a flask containing (EtCp) ₂ YCl at room temperature and stirred at room temperature for 12 hours. The mixture was evaporated under vacuum, dissolved in 250 ml of pentane, filtered, and the solvent and volatile substances were evaporated under vacuum. The resulting red liquid was obtained as a pink solid at 174°C and 36 mTorr. The yield was 69.9g (61.4%). The NMR (AV400MHz HD, Bruker company) analysis results are shown in Figure 4, and the characteristic peaks are as follows.

¹ H NMR (C ₆ D ₆ , 25°C): 0.96(t, 3H), 1.00(d, 6H), 1.12(s, 9H), 1.25(t, 6H), 2.08(q, 2H), 2.56( q, 4H), 3.38(m, 1H), 6.10(dt, 8H).

[Synthesis Example 4] Bis(diethylcyclopentadienyl)yttrium chloride [(Et ₂ CP) ₂ Synthesis of [YCl]

To a solution of 300 ml of THF and 62.59 g (0.512 mol) of diethylcyclopentadiene, 204.9 ml (0.512 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise at -78°C, stirred for 30 minutes, and then raised to room temperature. Then, the mixture was stirred for additional 2 hours to prepare a Li-Et ₂ Cp solution. 50.0 g (0.256 mol) of yttrium chloride and 150 ml of toluene were added to a new flask, and then cooled to -78°C while stirring. The previously prepared Li-Et ₂ Cp solution was slowly added dropwise to the flask containing the yttrium chloride mixture, stirred at -78°C for 30 minutes, then raised to room temperature and stirred for 12 hours to produce bis(diethylcyclopentadienyl)yttrium. Chloride was synthesized.

[Synthesis Example 5] Bis(diethylcyclopentadienyl)(isopropyl-tertiary butyl-methylamidinato)yttrium [(Et ₂ CP) ₂ Y( ⁱ Pr ^t Synthesis of [BuMe-AMD)]

Add 40.02 g (0.256 mol) of isopropyl-tertiary butyl-methylamidinate to 300 ml of THF, cool to -78°C, and then slowly add 102.4 ml (0.256 mol) of n-BuLi hexane solution (2.5 M) dropwise. Li-( ⁱ Pr ^t BuMe-AMD) was prepared. The solution was stirred at -78°C for 30 minutes, then warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-( ⁱ Pr ^t BuMe-AMD) solution was slowly added dropwise to a flask containing (Et ₂ Cp) ₂ YCl at room temperature and stirred at room temperature for 12 hours. The mixture was evaporated under vacuum, dissolved in 250 ml of pentane, filtered, and the solvent and volatile substances were evaporated under vacuum. The resulting brown solid was obtained at 200°C and 27 mTorr as a light pink solid. The yield was 94.2g (75.6%). The NMR (AV400MHz HD, Bruker company) analysis results are shown in Figure 5, and the characteristic peaks are as follows.

¹ H NMR (C ₆ D ₆ , 25°C): 1.02(d, 6H), 1.16(s, 9H), 1.26(m, 12H), 1.69(s, 3H), 2.55(m, 8H), 3.32( m, 1H), 6.00(m, 6H).

The light yellow solid left almost no residual mass at 1% during TGA (SDT Q600 from TA Instruments) analysis, which was measured at a temperature rise rate of 10°C/min in an atmosphere flowing nitrogen at 200 mL/min. These results are shown in Figure 6. The TGA analysis results showing the percentage of weight loss according to temperature change are shown in Figure 6.

The light yellow solid sample was placed in an airtight container for DSC and kept at 40℃ for 10 minutes, and then a decomposition peak was observed above 400℃ during DSC (Discovery 25, TA instrument) analysis measured at a temperature rise rate of 10℃/min. It has been done. These results are shown in Figure 7. The DSC analysis results showing the change in thermal energy according to the temperature change are shown in Figure 7.

[Synthesis Example 6] Bis(ethyl,methylcyclopentadienyl)yttrium chloride [(EtCp) ₂ Synthesis of [YCl]

To a solution of 300 ml of THF and 55.40 g (0.512 mol) of ethyl, methylcyclopentadiene, 204.9 ml (0.512 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise at -78°C, stirred for 30 minutes, and then cooled to room temperature. The temperature was raised and stirred for additional 2 hours to prepare a Li-EtMeCp solution. 50.0 g (0.256 mol) of yttrium chloride and 150 ml of toluene were added to a new flask, and then cooled to -78°C while stirring. The previously prepared Li-EtMeCp solution was slowly added dropwise to the flask containing the yttrium chloride mixture, stirred at -78°C for 30 minutes, then raised to room temperature and stirred for 12 hours to produce bis(ethylmethylcyclopentadienyl)yttrium chloride. synthesized.

[Synthesis Example 7] Bis(ethylmethylcyclopentadienyl)(diisopropyl-methylamidinato)yttrium[(Et ₂ CP) ₂ Y( ⁱ Pr ₂ Synthesis of [Me-AMD)]

Add 32.32 g (0.256 mol) of diisopropyl carbodiimide to 300 ml of THF and cool to -78°C. Then, 160.0 ml (0.256 mol) of MeLi diethyl solution (1.6 M) was slowly added dropwise to form Li-( ⁱ Pr ₂ Me-AMD) was prepared. The solution was stirred at -78°C for 30 minutes, then warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-( ^iPr ₂ Me-AMD) solution was slowly added dropwise to a flask containing (EtMeCp) ₂ YCl at room temperature and stirred at room temperature for 12 hours. The mixture was evaporated under vacuum, dissolved in 250 ml of pentane, filtered, and the solvent and volatile substances were evaporated under vacuum. A light yellow liquid was obtained as a red solid and liquid mixture at 210°C and 98 mTorr. The yield was 68.9g (56.9%). The NMR (AV400MHz HD, Bruker company) analysis results are shown in Figure 8, and the characteristic peaks are as follows.

¹ H NMR (C ₆ D ₆ , 25°C): 1.00(d, 12H), 1.21(m, 6H), 1.54(s, 3H), 2.119(m, 6H), 2.52(m, 4H), 3.31( m, 1H), 6.00(m, 6H).

Although the present invention has been described with reference to preferred embodiments as described above, it is not limited to the above embodiments and may be modified in various ways by those skilled in the art without departing from the spirit of the invention. and can be changed. Such modifications and variations should be considered to fall within the scope of the present invention and the appended claims.

Claims (16)

A precursor for forming a thin film, characterized in that it contains a compound represented by the following formula (1).

[Formula 1]


In Formula 1,
M is yttrium (Y) or scandium (Sc), and R ₁ to R ₈ are each independently a hydrogen atom, or a C ₁ -C ₆ straight-chain, branched or cyclic alkyl group, alkenyl group, alkoxy group, or amine group. Or it is a silyl group.
In claim 1,
In Formula 1, R ₆ and R ₈ are different C ₁ -C ₆ straight chain, branched or cyclic alkyl groups.
In claim 1,
A precursor for forming a thin film, wherein at least two of R ₁ to R ₅ in Formula 1 are different C ₁ -C ₆ straight-chain, branched, or cyclic alkyl groups.
In claim 1,
In Formula 1, R ₆ and R ₈ are different C ₁ -C ₆ linear, branched or cyclic alkyl groups, or at least two of R ₁ to R ₅ are different C ₁ -C ₆ straight alkyl groups. A precursor for forming a thin film, characterized in that it is a chain-shaped, branched, or cyclic alkyl group.
In claim 1,
A precursor for forming a thin film, wherein one or more of R ₁ to R ₅ in Formula 1 is an ethyl group (Et) or a methyl group (Me).
In claim 1,
In Formula 1, any one or more of R ₆ and R ₈ is a C ₁ -C ₆ branched alkyl group.
In claim 1,
In Formula 1, one or more of R ₆ and R ₈ are t-butyl group (t-Bu), s-butyl group (sec-Bu), isobutyl group (i-Bu), and isopropyl group (iPr). ), or a precursor for forming a thin film, characterized in that it is a t-amyl group.
In claim 1,
In Formula 1, one of R ₆ and R ₈ is a t-butyl group and the other is an isopropyl group.
In claim 1,
In Formula 1, R ₇ is an ethyl group (Et), n-propyl group (n-Pr), n-butyl group (n-Bu), isopropyl group (i-Pr), and s-butyl group (sec-Bu). Or a precursor for forming a thin film, characterized in that it is an isobutyl group (i-Bu).
A thin film forming method comprising a step of forming a thin film on a substrate using the thin film forming precursor according to any one of claims 1 to 9.
In claim 10,
The process of forming a thin film on the substrate is,
A process of forming a precursor thin film by depositing the thin film forming precursor on the surface of a substrate;
A process of reacting the precursor thin film with a reactive gas;
A thin film forming method comprising:
In claim 11,
The reactive gases include nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (N ₂ H ₄ ), nitrous oxide (N ₂ O), oxygen (O ₂ ), water vapor (H ₂ O), and ozone (O ₃ ). , Hydrogen peroxide (H ₂ O ₂ ), silane, hydrogen (H ₂ ), and diborane (B ₂ H ₆ ). A method of forming a thin film, characterized in that one or more of the following.
In claim 11,
The process of forming the precursor thin film includes vaporizing the precursor for forming the thin film and transferring it into the chamber.
In claim 11,
The deposition includes a spin-on dielectric (SOD) process, a low temperature plasma (LTP) process, a chemical vapor deposition (CVD) process, and a plasma enhanced chemical vapor deposition (PECVD) process. process, High Density Plasma -Chemical Vapor Deposition (HDPCVD) process, Atomic Layer Deposition (ALD) process, or Plasma-Enhanced Atomic Layer Deposition (PEALD) process. A thin film forming method characterized in that it is carried out by one.
In claim 10,
The process of forming a thin film on the substrate is,
A thin film forming method comprising supplying the thin film forming precursor to a substrate and applying plasma to form a thin film.
A semiconductor device comprising a thin film manufactured by the thin film forming method of claim 10.