KR20230158682A - Novel Organo-Tin Compounds and Method for deposition of thin film using the same - Google Patents

Abstract

The present invention relates to a novel tin precursor with improved thermal stability and volatility, and provides a method for easily producing a high-quality tin nitride thin film with an excellent growth rate at a low temperature using the tin precursor, and a thin film manufactured thereby. can do.

Description

Novel Organo-Tin Compounds and Method for deposition of thin film using the same}

The present invention relates to an organotin compound and a method of manufacturing a thin film using the same. More specifically, it relates to a novel organotin compound and a method of manufacturing a thin film using the same for forming a tin nitride thin film.

Currently synthesized binary tin compounds include compounds containing post-transition metals, solid-state oxides (Sn ₅ O ₆ , Sn ₃ O ₄ , Sn ₂ O ₃ , SnO, SnO ₂ ), and sulfides (Sn ₃ S, SnS, Sn ₂ S ₃ , SnS ₂ , Sn ₃ S ₇ ), fluoride (Sn ₃ F ₈ , SnF ₂ , SnF ₃ ) are manufactured in the form of transparent electronic devices, batteries, etc. It is used in many solid state applications such as photocatalysis, photovoltaic absorber, antibacterial coating, contact, dentistry, etc. for this purpose, various tin organic compounds containing appropriate organic ligands are used. Metal compounds can be used.

Their composition is mainly due to the tendency of tin to determine three oxidation states: Sn(0), Sn(II) and Sn(IV), which are thermodynamically stable at ambient conditions; Binary, ternary and higher nitrides are thermodynamically less stable than the corresponding metal oxides.

Nitride materials are often affected in the atmosphere, causing deterioration of the compound such as oxidation or hydrolysis, but in particular, III-N compound semiconductors such as GaN, InN, and AlN have a band gap of 0.7 eV (InN) up to 6.2 eV. Since (AlN) can be tuned, tuning the band profile and consequently the properties of the device is a very attractive exploration in the field of field effect transistors, light emitting diodes and lasers. As the gradual research and development related to the usefulness of nitrides progresses, the kinetic and technical stability of the compounds to the surrounding environment is becoming increasingly important.

In general, tin nitride has hitherto charge balanced Sn ₃ N ₄ ; Three metastable compounds are proposed: Sn(IV), mixed-valent SnN containing Sn(II/IV), and high-pressure pernitride SnN ₂ phase containing Sn(IV). However, pure divalent binary tin nitride has only revealed several structures using a calculation database and has not yet been experimentally realized, and Sn ₃ N ₂ is a candidate.

Meanwhile, chemical vapor deposition (CVD) or atomic layer deposition (ALD) has been used as a process for forming a nitride thin film containing a tin component. However, when manufacturing a tin thin film by the chemical vapor deposition (CVD) or atomic layer deposition (ALD) process as described above, there are differences in the degree of deposition, deposition control characteristics, crystallinity, purity, etc. of the formed nitride thin film depending on the characteristics of the metal precursor. Because this occurs, the development of metal precursors with excellent properties is necessary.

As a prior art for precursors for producing such tin nitride thin films, Japanese Patent Publication No. 2009-227674 discloses divalent tin complexes and tin aminoalkoxide complexes as precursors for thin films of tin components, and tin amino In the alkoxide complex, by coordinating a dialkylamino group to tin as a ligand, not only does it not cause carbon or halogen contamination, improving thermal stability and volatility, but it can also easily form a thin film of tin and tin oxide even at a lower temperature. The existing technology has been revised, and in Korean Patent Publication No. 2022-0041112, bis(ethylcyclopentadienyl)tin is disclosed as a precursor for tin and tin oxide thin films.

However, since the tin precursors described in the prior literature contain only intramolecular tin components, in order to manufacture tin nitride thin films using them, a separate nitrogen source such as ammonia gas must be introduced in addition to the tin precursor. In this case, In manufacturing a tin nitride (Sn ₃ N ₄ ) thin film, thermal stability cannot be secured during the reaction between the tin precursor and ammonia, making it difficult to apply to the mass production process through mass synthesis.

In other words, the reaction between a metal compound and ammonia, a representative material for making nitrides, is thermally very unstable with respect to elements or intermetallic compounds, which is an obstacle to the mass synthesis of nitrides targeting two binary nitrides, and the reaction A large amount of thermal energy is required to overcome the activation barrier, and thermally unstable binary nitrides such as Na ₃ N and Sn ₃ N ₄ are avoided in this reaction.

Meanwhile, research on the synthesis of a single-source precursor containing nitrogen (N) in an organic tin precursor that may not use a separate nitrogen source such as ammonia gas is insufficient.

Therefore, it can be used for forming tin nitride thin films, and when manufacturing metal thin films or metal nitride thin films, it can be easily processed at low temperatures and can be a new precursor with improved thermal stability, volatility, and deposition rate of tin metal. There is a continued need for development of organic tin compounds and processes for manufacturing thin films with improved physical properties using the same.

Japanese Patent Publication No. 2009-227674 (2009.10.08.) Korean Patent Publication No. 2022-0041112 (2022.03.31)

The present invention is intended to solve the above problems, and is the first technical aim to provide a novel tin compound as a single-source precursor, with improved thermal stability and volatility, and capable of easily producing high-quality tin nitride thin films at low temperatures. Make it an assignment.

In addition, another object of the present invention is to provide a novel method for producing the organic tin compound and a method for producing a tin nitride thin film using the same.

In order to achieve the above object, the present invention provides an organic tin compound represented by the following [Chemical Formula A].

[Formula A]

In Formula A,

R ₂ to R ₇ , R ₁₂ to R ₁₇ are each the same or different and independently of each other hydrogen, deuterium, C ₁ -C ₆ linear, branched or cyclic alkyl group; and C ₁ -C ₆ linear, branched or cyclic halogenated alkyl groups; Any one selected from,

R ₁ and R ₁₁ are each the same or different and independently of each other a C ₁ -C ₁₀ linear, branched or cyclic alkyl group; and a C ₁ -C ₁₀ linear, branched or cyclic halogenated alkyl group,

The m and n are each the same or different and are independently any integer selected from 1 to 3,

When m is 2 or more, each ' ' is the same or different,

In addition, when n is 2 or more, each ' ' is the same or different.

In one embodiment, R ₂ to R ₇ , R ₁₂ to R ₁₇ may each be the same or different and independently selected from hydrogen, deuterium, CH ₃ , C ₂ H ₅ , CH(CH ₃ ) ₂ and C(CH ₃ ) ₃ .

In one embodiment, R ₁ and R ₁₁ are each the same or different and independently of each other, a C ₁ -C ₆ linear alkyl group; C ₁ -C ₆ linear halogenated alkyl group; C ₃ -C ₆ branched or cyclic alkyl group; and C ₃ -C ₆ branched or cyclic halogenated alkyl group; It may be any one selected from among.

In one embodiment, R ₁ and R ₁₁ may be the same or different and independently selected from CH ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ there is.

In one embodiment, m and n may each be 1 or 2.

In one embodiment, R ₂ to R ₇ , R ₁₂ to R ₁₇ may be the same or different and independently of each other, hydrogen or deuterium.

In one embodiment, the two ligands coordinated to the tin may be identical to each other.

Additionally, the present invention provides a method for producing a tin nitride thin film using the organic tin compound as a precursor.

In one embodiment, the process of growing the tin nitride thin film may be performed by chemical vapor deposition (CVD), atomic layer deposition (ALD), or a solution process.

Additionally, the present invention relates to a tin compound represented by compound B below; A nitrogen-containing ring compound represented by the following compound C1; and a nitrogen-containing ring compound represented by Compound C2; and a nitrogen-containing ring compound represented by Compound C2, respectively.

[Compound B]

[Compound C1] [Compound C2]

[Formula A]

In the compound B,

R ₃₁ to R ₃₄ are the same or different and independently of each other, a C ₁ -C ₁₅ linear, branched or cyclic alkyl group, a C ₆ -C ₁₈ aryl group, or a C ₃ -C ₁₅ linear or branched alkyl group. Or any one selected from cyclic alkylsilyl group and C ₆ -C ₁₈ arylsilyl group,

In Compound C1, Compound C2 and Formula A, R ₁ to R ₇ , R ₁₁ to R ₁₇ , m and n are each as previously defined.

Since the tin precursor represented by formula A of the present invention has improved thermal stability and volatility, a large-area and highly uniform tin nitride thin film can be easily and stably manufactured using it.

The tin precursor according to the present invention contains both a tin component and a nitrogen component in one molecule, so when used as a precursor for forming a tin nitride thin film, tin nitride is formed even without adding a separate nitrogen precursor component such as ammonia gas. A thin film can be easily formed.

Figure 1 is a diagram showing the X-ray single crystal structure of a tin precursor prepared according to Synthesis Example 5.
Figure 2 is a diagram showing the X-ray single crystal structure of the tin precursor prepared according to Synthesis Example 7.
Figure 3 is a diagram showing the X-ray single crystal structure of the tin precursor prepared according to Synthesis Example 8.
Figure 4 is a diagram showing the results of thermogravimetric analysis (TGA) of tin precursors prepared according to Synthesis Examples 5 to 8.

Hereinafter, the present invention will be described in more detail. Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout the specification of the present application, when a part "includes" a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary.

In order to achieve the above technical problems, the present invention discovered that a large-area and highly uniform tin nitride thin film can be produced when using a tin compound in which a nitrogen-containing organic ligand having a specific structural formula is coordinated to tin. was able to complete.

Hereinafter, the organic tin compound according to the present invention and the method of manufacturing a tin nitride thin film using the same will be described in more detail.

The present invention provides an organic tin compound represented by the following [Chemical Formula A].

[Formula A]

In Formula A,

Substituents R ₂ to R ₇ , R ₁₂ to R ₁₇ are each the same or different and independently of each other hydrogen, deuterium, C ₁ -C ₆ linear, branched or cyclic alkyl group; and C ₁ -C ₆ linear, branched or cyclic halogenated alkyl groups; Any one selected from,

R ₁ and R ₁₁ are each the same or different and independently of each other a C ₁ -C ₁₀ linear, branched or cyclic alkyl group; and a C ₁ -C ₁₀ linear, branched or cyclic halogenated alkyl group,

The m and n are each the same or different and are independently any integer selected from 1 to 3,

When m is 2 or more, each ' ' is the same or different,

In addition, when n is 2 or more, each ' ' is the same or different.

The compound represented by the formula A according to the present invention corresponds to an organic tin complex in which a cyclic amine ligand containing two nitrogen atoms, each identical or different, is coordinated to the central tin atom, and the organic tin complex is a chemical vapor. When used as a precursor to form a thin film for deposition or atomic layer deposition, it can have excellent chemical and thermal stability, thereby providing a high-quality, large-area and highly uniform tin nitride thin film.

Here, in the cyclic amine ligand coordinated to the central tin atom in the organotin compound of the present invention, the hydrogen of the nitrogen atom bonded to R1 is removed or bonded to R11 through a dehydrogenation reaction from Compound C1 and Compound C2 below. It can act as a ligand by removing the hydrogen from the nitrogen atom.

[Compound C1] [Compound C2]

In addition, in the organotin compound according to the present invention, R ₂ to R ₇ , which are substituents in the nitrogen-containing heterocyclic ligand derived from the compound C1 and compound C2 in [Formula A], R ₁₂ to R ₁₇ are preferably any one selected from hydrogen, deuterium, CH ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ , and in this case, excellent chemical-thermal stability Since it can have a fast deposition rate of a thin film even at a relatively low temperature, it can have very desirable properties as a precursor for forming a tin nitride thin film.

In addition, in the organotin compound according to the present invention, the substituents R ₁ and R ₁₁ are each the same or different and independently from each other a linear alkyl group of C ₁ -C ₆ ; C ₁ -C ₆ linear halogenated alkyl group; C ₃ -C ₆ branched or cyclic alkyl group; and C ₃ -C ₆ branched or cyclic halogenated alkyl group; It may be any one selected from among, and more preferably, R ₁ and R ₁₁ are each the same or different and independently of each other, CH ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) It is preferably any one selected from among _{the three} , and in this case, it has excellent chemical-thermal stability and has a fast deposition rate of the thin film even at a relatively low temperature, so it is very desirable as a precursor for forming a tin nitride thin film. It can have character.

In addition, in one embodiment of the present invention, m and n in the nitrogen-containing heterocyclic ligand derived from the compound C1 and compound C2 in [Formula A] may be 1 or 2, respectively, and through this, the nitrogen-containing heterocyclic ligand may be The cyclic ligand structure can exhibit a stable state by forming a 5-membered ring or 6-membered ring structure.

In addition, as a more preferred embodiment of the present invention, the substituents R ₂ to R ₇ R ₁₂ to R ₁₇ may be the same or different and independently of each other, hydrogen or deuterium.

In addition, as a more preferred embodiment of the present invention, the two nitrogen-containing heterocyclic ligands derived from Compound C1 and Compound C2 in [Formula A], which are coordinated to the tin, may be identical to each other, and in this case, Since the manufacturing process of the tin complex is simple and the ligand coordinated to tin is the same, it has the advantage of reducing process variables according to a more simplified mechanism when forming a thin film than when using different ligands when forming a thin film.

Meanwhile, the present invention can provide a method of manufacturing a tin nitride thin film by using the organic tin compound represented by Formula A as a precursor, and in this case, the process of growing the tin nitride thin film is chemical vapor deposition (CVD). Alternatively, it may be performed by atomic layer deposition (ALD) or a solution process.

Meanwhile, the organic tin compound represented by the formula A according to the present invention contains a total of four nitrogen atoms in two ligands coordinated to tin atoms in the molecule, and thus can form a tin nitride thin film without adding additional nitrogen components such as ammonia gas. It can have the advantage of being able to be easily formed.

Here, in the chemical vapor deposition (CVD) method, atomic layer deposition (ALD) or solution process, the present invention appropriately adjusts the growth rate and thin film formation temperature conditions according to each process condition to optimize the Tin nitride thin films with a thickness and density of can be manufactured.

More specifically, when using the chemical vapor deposition (CVD) method, a reactant containing the organic tin compound precursor of the present invention is supplied in a gaseous state to a reactor containing a substrate having various types or shapes, thereby forming a tin layer on the substrate. A nitride thin film can be formed. In this case, since the tin compound represented by the formula A of the present invention is thermally stable and has good volatility, a tin nitride thin film of a desired shape can be manufactured under various conditions.

In addition, in the present invention, when using atomic layer deposition (ALD), a reactant containing the organic tin compound represented by formula A in the present invention as a precursor is supplied to the deposition chamber in pulse form under reduced pressure or high vacuum. Thus, a precise single layer film can be formed while causing a chemical reaction with the surface of a substrate such as a wafer.

Meanwhile, the present invention relates to a tin compound represented by compound B below; A nitrogen-containing ring compound represented by the following compound C1; and a nitrogen-containing ring compound represented by Compound C2; and a nitrogen-containing ring compound represented by Compound C2, respectively.

[Compound B]

[Compound C1] [Compound C2]

[Formula A]

In the compound B,

R ₃₁ to R ₃₄ are the same or different and independently of each other, a C ₁ -C ₁₅ linear, branched or cyclic alkyl group, a C ₆ -C ₁₈ aryl group, or a C ₃ -C ₁₅ linear or branched alkyl group. Or any one selected from cyclic alkylsilyl group and C ₆ -C ₁₈ arylsilyl group,

In Compound C1, Compound C2 and Formula A, R ₁ to R ₇ , R ₁₁ to R ₁₇ , m and n are each as defined above.

That is, the organic tin compound represented by formula A of the present invention is an amine ligand containing R ₃₁ and R ₃₂ in the tin compound represented by compound B below, and instead of the amine ligand containing R ₃₃ and R ₃₄ , the above compound Compound represented by C1; and a compound represented by compound C2; are used as reactants, respectively, to coordinate the nitrogen-containing heterocyclic ligand derived from compound C1 and compound C2 to a tin atom, thereby preparing an organic tin compound represented by [Formula A]. You can.

Here, the substituents R ₂ to R ₇ in the formulas C1 and C2 according to the present invention, R ₁₂ to R ₁₇ are each the same or different and independently of each other hydrogen, deuterium, C ₁ -C ₆ linear, branched or cyclic alkyl group; and C ₁ -C ₆ linear, branched or cyclic halogenated alkyl groups; It may be any one selected from among, preferably, any one selected from hydrogen, deuterium, CH ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ , and R ₁ and R ₁₁ are each the same or different and independently of each other, and are each the same or different and independently of each other, a linear alkyl group of C ₁ -C ₆ ; C ₁ -C ₆ linear halogenated alkyl group; C ₃ -C ₆ branched or cyclic alkyl group; and C ₃ -C ₆ branched or cyclic halogenated alkyl group; Any one selected from among can be used, and more preferably, R ₁ and R ₁₁ are the same or different and independently of each other, CH ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) It may be any one selected from ₃ .

In addition, m and n in the formulas C1 and C2 are the same or different, and may independently be any integer selected from 1 to 3. Preferably, m and n may be 1 or 2, respectively. there is.

Here, when an organic solvent is used in producing the organic tin compound represented by the formula A, suitable types of organic solvents include hexane, toluene, tetrahydrofuran, hexane, cyclohexane, diethyl ether, etc. However, it is not limited to this, and hexane, toluene, or cyclohexane can be preferably used.

The reaction conditions for preparing the organic tin compound represented by the formula A are preferably in the organic solvent, mixing each reactant at a temperature range of 0 to 100° C., preferably 10 to 40° C., for 12 to 24 hours. The reaction can proceed through stirring, and through this, an organic tin compound represented by the formula A can be produced.

At this time, in order to separate the product from the by-products or unreacted products generated during the reaction, recrystallization, sublimation, distillation, extraction, or column chromatography is used to produce a high-purity, novel product. Organic tin compounds can be obtained.

The high-purity organotin compound represented by Chemical Formula A thus obtained may be solid or liquid at room temperature, and is thermally stable and has good volatility.

The present invention can be better understood by the following examples, which are for illustrative purposes only and are not intended to limit the scope of protection defined by the appended claims.

(1) Preparation of amine compounds for nitrogen-containing organic ligands

[Scheme 1]

Synthesis Example 1: N -(tert-butyl)-3,4-dihydro-2H-pyrrol-5-amine(tbip)

In a pressure reaction flask, 5-ethoxy-3,4-dihydro-2H-pyrrole (1.00 g, 8.84 mmol, 1.0 equiv.) was dissolved in ethanol and stirred at room temperature while tert-butylamine hydrochloride (0.97 g, 8.84 mmol, 1.0 equiv.) and tert-butylamine (1.86 mL, 17.7 mmol, 2.0 equiv.) were added and stirred for an additional 30 minutes, and then stirred at 130°C for 2 days. When the reaction was completed, it was cooled to room temperature, and by-products were removed under reduced pressure. After adjusting the reaction temperature to 0°C using a cooling bath, 6 M NaOH aqueous solution was slowly added and stirred for an additional hour. The reactant was separated into two layers using diethyl ether and deionized water (H ₂ O), the organic layer was extracted using a separatory funnel, and the remaining moisture was removed with magnesium sulfate (MgSO ₄ ). Filter filtered. The obtained filtrate was concentrated under reduced pressure, and a white solid compound was obtained. This solid was sublimated under reduced pressure at 50°C and 8 mbar to obtain a pure compound, N -(tert-butyl)-3,4-dihydro-2H-pyrrol-5-amine. (0.84 g, yield 68%)

¹ H NMR (500 MHz, Benzene- d ₆ ) δ (ppm): δ 3.79 (t, J = 6.9 Hz, 2H), 3.49 (s, 1H), 1.94 (t, J = 8.2 Hz, 2H), 1.59 ?? 1.52 (m, 2H), 1.38 (s, 9H).

¹³ C NMR (101 MHz, Benzene- d ₆ ) δ (ppm): δ 163.34, 58.74, 51.15, 34.78, 29.13, 23.17.

Synthesis Example 2: N -(tert-butyl)-2-methyl-3,4-dihydro-2H-pyrrol-5-amine(tbmp):

5-ethoxy-2-methyl-3,4-dihydro-2H-pyrrole (1.00 g, 7.86 mmol, 1.0 equiv.) was dissolved in ethanol in a pressure reaction flask and stirred at room temperature while tert- Butylamine hydrochloride (0.86 g, 7.86 mmol, 1.0 equiv.) and tert-butylamine (1.65 mL, 15.7 mmol, 2.0 equiv.) were added and stirred for an additional 30 minutes, and then stirred at 130°C for 2 days. When the reaction was completed, it was cooled to room temperature, and by-products were removed under reduced pressure. After adjusting the reaction to 0°C using a cooling bath, 6 M NaOH aqueous solution was slowly added and stirred for an additional hour. The reactant was separated into two layers using diethyl ether (Ether) and deionized water (H ₂ O), the organic layer was extracted using a separatory funnel, residual moisture was removed with magnesium sulfate (MgSO ₄ ), and filtered. Filtered. The obtained filtrate was concentrated under reduced pressure, and a white solid compound was obtained. This solid was sublimated under reduced pressure at 50°C and 8 mbar to obtain a pure compound, N -(tert-butyl)-2-methyl-3,4-dihydro-2H-pyrrol-5-amine. (1.05 g, yield 86%)

¹ H NMR (400 MHz, Benzene- d ₆ ) δ (ppm): δ 4.04 (h, J = 6.6 Hz, 1H), 3.42 (s, 1H), 2.02 (t, J = 7.9 Hz, 2H), 1.84 ?? 1.76 (m, 1H), 1.36 (s, 9H), 1.29 (d, J = 6.6 Hz, 3H), 1.21 ?? 1.12 (m, 1H).

¹³ C NMR (101 MHz, Benzene- d ₆ ) δ (ppm): δ 162.17, 65.53, 51.14, 35.11, 31.22, 29.08, 24.05.

HR-MS: [M] ⁺ Calculated: (C ₉ H ₁₈ N ₂ ) 154.1470; Found: 154.1470

Synthesis Example 3: N -(tert-butyl)-3,4,5,6-tetrahydropyridin-2-amine(tbtp)

In a pressure reaction flask, 6-ethoxy-2,3,4,5-tetrahydropyridine (1.00 g, 7.86 mmol, 1.0 equiv.) was dissolved in ethanol and stirred at room temperature while tert-butylamine hydrochloride (0.86 g, 7.86 mmol, 1.0 equiv.) and tert-butylamine (1.65 mL, 15.7 mmol, 2.0 equiv.) were added and stirred for an additional 30 minutes, and then stirred at 130°C for 2 days. When the reaction was completed, it was cooled to room temperature, and by-products were removed under reduced pressure. After adjusting the reaction to 0°C using a cooling bath, 6 M NaOH aqueous solution was slowly added and stirred for an additional hour. The reactant was separated into two layers using diethyl ether (Ether) and deionized water (H ₂ O), the organic layer was extracted using a separatory funnel, residual moisture was removed with magnesium sulfate (MgSO ₄ ), and filtered. Filtered. The obtained filtrate was concentrated under reduced pressure, and a white solid compound was obtained. This solid was distilled under reduced pressure at 50°C and 8 mbar to obtain a pure compound, N -(tert-butyl)-3,4,5,6-tetrahydropyridin-2-amine. (0.90 g, yield 74%)

¹ H NMR (400 MHz, Benzene- d ₆ ) δ (ppm): δ 3.54 (t, J = 5.7 Hz, 2H), 3.09 (s, 1H), 1.61 (t, J = 6.3 Hz, 2H), 1.44 ?? 1.39 (m, 11H), 1.35 ?? 1.31 (m, 2H).

¹³ C NMR (101 MHz, Benzene- d ₆ ) δ (ppm): δ 154.45, 50.59, 47.08, 29.47, 27.47, 23.31, 21.09.

HR-MS: [M] ⁺ Calculated: (C ₉ H ₁₈ N ₂ ) 154.1470; Found: 154.1470

Synthesis Example 4: N -(tert-butyl)-3,4,5,6-tetrahydro-2H-azepin-7-amine(tbta)

7-ethoxy-3,4,5,6-tetrahydro-2H-azepine (1.00 g, 7.08 mmol, 1.0 equiv.) was dissolved in ethanol in a pressure reaction flask and stirred at room temperature while tert- Butylamine hydrochloride (0.78 g, 7.08 mmol, 1.0 equiv.) and tert-butylamine (1.49 mL, 14.2 mmol, 2.0 equiv.) were added and stirred for an additional 30 minutes, and then stirred at 130°C for 2 days. When the reaction was completed, it was cooled to room temperature, and by-products were removed under reduced pressure. After adjusting the reaction to 0°C using a cooling bath, 6 M NaOH aqueous solution was slowly added and stirred for an additional hour. The reactant was separated into two layers using diethyl ether (Ether) and deionized water (H ₂ O), the organic layer was extracted using a separatory funnel, residual moisture was removed with magnesium sulfate (MgSO ₄ ), and filtered. Filtered. The obtained filtrate was concentrated under reduced pressure, and a white solid compound was obtained. This solid was sublimated under reduced pressure at 65°C and 8 mbar to obtain a pure compound, N -(tert-butyl)-3,4,5,6-tetrahydro-2H-azepin-7-amine.

¹ H NMR (400 MHz, Benzene- d ₆ ) δ (ppm): 3.55 ?? 3.53 (m, 2H), 1.76 ?? 1.74 (m, 2H), 1.53 (hept, J = 4.0, 3.2 Hz, 4H), 1.42 (s, 9H), 1.27 (h, J = 5.1, 3.5 Hz, 2H).

¹³ C NMR (101 MHz, Benzene- d ₆ ) δ (ppm): 162.24, 50.72, 50.13, 34.36, 31.53, 29.46, 29.09, 25.24.

HR-MS: [M] ⁺ Calculated: (C ₁₀ H ₂₀ N ₂ ) 168.1626; Found: 168.1612

(2) Preparation of organic tin complex (precursor)

[Scheme 2]

Synthesis Example 5: Sn(tbip) ₂ (tbip: N -(tert-butyl)-3,4-dihydro-2H-pyrrol-5-amine)

Sn(btsa) ₂ (btsa: bis(trimethylsilyl)amide) (1.00 g, 2.28 mmol, 1.0 equiv.) was dissolved in toluene in a round bottom flask and stirred at room temperature, then tbip (0.64 g, 4.56 mmol) , 2.0 equiv.) was slowly added and stirred for 12 hours. When the reaction was completed, the by-products were removed under reduced pressure to obtain a white solid compound. This solid was recrystallized at room temperature to obtain tin complex (Sn(tbip) ₂ ), a pure transparent compound. (0.84 g, 97% yield)

¹ H NMR (500 MHz, Benzene- d ₆ ) δ (ppm): δ 3.33 (t, J = 6.8 Hz, 4H), 2.05 (t, J = 7.8 Hz, 4H), 1.59 (p, J = 7.4 Hz) , 4H), 1.31 (s, 18H).

¹³ C NMR (101 MHz, Benzene- d ₆ ) δ (ppm): δ 174.72, 51.34, 47.97, 31.63, 30.33, 25.34.

Anal. Calcd. for C ₁₆ H ₃₀ N ₄ Sn: C, 48.39; H, 7.61; N, 14.11. Found: C, 48.02; H, 7.70; N, 13.71.

HR-MS: [M] ⁺ Calculated: (C ₁₆ H ₃₀ N ₄ Sn) 398.1492; Found: 398.1483

Synthesis Example 6: Sn(tbmp) ₂ (tbmp: N -(tert-butyl)-2-methyl-3,4-dihydro-2H-pyrrol-5-amine)

Sn(btsa) ₂ (btsa: bis(trimethylsilyl)amide) (1.00 g, 2.28 mmol, 1.0 equiv.) was dissolved in toluene in a round bottom flask and stirred at room temperature, then tbmp (0.70 g, 4.56 mmol) , 2.0 equiv.) was slowly added and stirred for 12 hours. When the reaction was completed, by-products were removed under reduced pressure to obtain a pure solid compound Sn(tbmp) ₂ . (0.93 g, 99% yield)

¹ H NMR (500 MHz, Benzene- d ₆ ) δ (ppm): δ 3.81 ?? 3.66 (m, 2H), 2.28 ?? 2.18 (m, 2H), 2.15 ?? 2.01 (m, 2H), 1.87 ?? 1.74 (m, 2H), 1.31 ?? 1.30 (m, 18H), 1.28 ?? 1.24 (m, 2H), 1.14 (dd, J = 8.6, 6.3 Hz, 6H).

¹³ C NMR (101 MHz, Benzene- d ₆ ) δ (ppm): δ 174.42, 174.22, 55.35, 55.26, 51.97, 51.87, 33.37, 32.92, 32.13, 32.08, 30.54, 30.10, 24.27 , 23.99.

HR-MS: [M] ⁺ Calculated: (C ₁₈ H ₃₄ N ₄ Sn) 426.1805; Found: 426.1810

Anal. Calcd. for C ₁₈ H ₃₄ N ₄ Sn: C, 50.85; H, 8.06; N, 13.18. Found: C, 50.84; H, 8.21; N, 13.39.

Synthesis Example 7: Sn(tbtp) ₂ (tbtp: N -(tert-butyl)-3,4,5,6-tetrahydropyridin-2-amine)

Sn(btsa) ₂ (btsa: bis(trimethylsilyl)amide) (1.00 g, 2.28 mmol, 1.0 equiv.) was dissolved in toluene in a round bottom flask and stirred at room temperature, then tbtp (0.70 g, 4.56 mmol) , 2.0 equiv.) was slowly added and stirred for 12 hours. When the reaction was completed, the by-products were removed under reduced pressure to obtain a white solid compound. This solid was recrystallized at room temperature to obtain Sn(tbtp) ₂ compound, a pure transparent compound. (0.91 g, 97% yield)

¹ H NMR (500 MHz, Benzene- d ₆ ) δ (ppm): δ 3.47 (t, J = 5.5 Hz, 4H), 2.14 (t, J = 6.0 Hz, 4H), 1.34 ?? 1.29 (m, 26H).

¹³ C NMR (126 MHz, Benzene- d ₆ ) δ (ppm): δ 166.65, 51.42, 45.40, 32.46, 29.51, 24.59, 20.82.

HR-MS: [M] ⁺ Calculated: (C ₁₈ H ₃₄ N ₄ Sn) 426.1805; Found: 426.1797

Anal. Calcd. for C ₁₈ H ₃₄ N ₄ Sn: C, 50.85; H, 8.06; N, 13.18. Found: C, 50.53; H, 8.11; N, 12.96.

Synthesis Example 8: Sn(tbta) ₂ (tbta: N -(tert-butyl)-3,4,5,6-tetrahydro-2H-azepin-7-amine)

Sn(btsa) ₂ (btsa: bis(trimethylsilyl)amide) (1.00 g, 2.28 mmol, 1.0 equiv.) was dissolved in toluene in a round bottom flask and stirred at room temperature, then tbta (0.77 g, 4.56 mmol) , 2.0 equiv.) was slowly added and stirred for 12 hours. When the reaction was completed, the by-products were removed under reduced pressure to obtain a white solid compound. This solid was recrystallized at room temperature to obtain Sn(tbta) ₂ compound, a pure transparent compound. (1.01 g, 98% yield)

¹ H NMR (500 MHz, Benzene- d ₆ ) δ (ppm): δ 3.47 (dd, J = 6.1, 2.9 Hz, 4H), 2.24 ?? 2.22 (m, 4H), 1.51 ?? 1.42 (m, 12H), 1.31 (s, 18H).

¹³ C NMR (126 MHz, Benzene- d ₆ ) δ (ppm): δ 173.75, 51.33, 46.77, 32.83, 31.90, 31.45, 31.23, 25.10.

HR-MS: [M] ⁺ Calculated: (C ₂₀ H ₃₈ N ₄ Sn) 454.2118; Found:454.2119

Anal. Calcd. for C ₂₀ H ₃₈ N ₄ Sn: C, 53.00; H, 8.45; N, 12.36. Found: C, 52.74; H, 8.66; N, 12.21.

Experimental Example 1: X-ray single crystal structure analysis of tin precursor material

In order to confirm the solid phase molecular structure of the tin complex synthesized in Synthesis Example 5, Synthesis Example 7, and Synthesis Example 8, the single crystal structure was confirmed using a Bruker SMART APEX II X-ray Diffractometer to confirm the exact structure of the tin precursor compound. and these structures are shown in Figures 1 to 3, respectively.

Experimental Example 2: Thermogravimetric Analysis (TGA)

In order to confirm the thermal stability, volatility, and thermal decomposition temperature of the tin precursor compounds synthesized in Synthesis Examples 5 to 8, thermogravimetric analysis (TGA) was performed using NETZSCH TG 209 F3 thermogravimetry, and the results were is shown in Figure 4.

The thermogravimetric analysis (TGA) was measured while heating to 500°C at a rate of 20 K per minute in an argon gas atmosphere, and the compound to be analyzed generally gradually decreases in mass at around 105°C and rapidly decreases in mass at other temperatures. and the final residual amount of each compound to be analyzed (Sn(tbip) ₂ , 6.8 %; Sn(tbmp) ₂ , 3.7 %; Sn(tbtp) ₂ , 2.4 %; Sn(tbta) ₂ , 2.7 %) was confirmed. did. This shows that the novel tin complex (precursor) according to the present invention has excellent properties for forming a tin thin film or tin nitride thin film.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements can be made by those skilled in the art using the basic concept of the present invention as defined in the following claims. It falls within the scope of invention rights.

Claims (10)

An organic tin compound represented by the following [Chemical Formula A].
[Formula A]

In Formula A,
R ₂ to R ₇ , R ₁₂ to R ₁₇ are each the same or different and independently of each other hydrogen, deuterium, C ₁ -C ₆ linear, branched or cyclic alkyl group; and C ₁ -C ₆ linear, branched or cyclic halogenated alkyl groups; Any one selected from,
R ₁ and R ₁₁ are each the same or different and independently of each other a C ₁ -C ₁₀ linear, branched or cyclic alkyl group; and a C ₁ -C ₁₀ linear, branched or cyclic halogenated alkyl group,
The m and n are each the same or different and are independently any integer selected from 1 to 3,
When m is 2 or more, each ' ' is the same or different,
In addition, when n is 2 or more, each ' ' is the same or different.
According to paragraph 1,
R ₂ to R ₇ , R ₁₂ to R ₁₇ are each the same or different and independently selected from hydrogen, deuterium, CH ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ Organic tin compounds.
According to paragraph 1,
R ₁ and R ₁₁ are each the same or different and independently from each other a linear alkyl group of C ₁ -C ₆ ; C ₁ -C ₆ linear halogenated alkyl group; C ₃ -C ₆ branched or cyclic alkyl group; and C ₃ -C ₆ branched or cyclic halogenated alkyl group; An organic tin compound, characterized in that it is any one selected from among.

According to paragraph 3,
Wherein R ₁ and R ₁₁ are each the same or different and independently from each other, CH ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) _3. An organic tin compound, characterized in that .
According to paragraph 1,
An organic tin compound wherein m and n are each 1 or 2.
According to clause 5,
R ₂ to R ₇ , An organic tin compound wherein R ₁₂ to R ₁₇ are the same or different and independently of each other, hydrogen or deuterium.
According to paragraph 1,
An organic tin compound, wherein the two ligands coordinated to tin are identical to each other.
A method of producing a tin nitride thin film using any one organic tin compound selected from claims 1 to 7 as a precursor.
According to clause 8,
A method of manufacturing a tin nitride thin film, wherein the process of manufacturing the tin nitride thin film is performed by chemical vapor deposition (CVD), atomic layer deposition (ALD), or a solution process.
A tin compound represented by compound B below; A nitrogen-containing ring compound represented by the following compound C1; and a nitrogen-containing ring compound represented by compound C2; A method for producing an organic tin compound represented by formula A of claim 1, characterized in that the organic tin compound represented by formula A is prepared using each as a reactant.
[Compound B]

[Compound C1] [Compound C2]

[Formula A]

In the compound B,
R ₃₁ to R ₃₄ are the same or different and independently of each other, a C ₁ -C ₁₅ linear, branched or cyclic alkyl group, a C ₆ -C ₁₈ aryl group, or a C ₃ -C ₁₅ linear or branched alkyl group. Or any one selected from cyclic alkylsilyl group and C ₆ -C ₁₈ arylsilyl group,
R ₁ to R ₇ , R ₁₁ to R ₁₇ , m and n in Compound C1, Compound C2 and Formula A are each as defined in paragraph 1 above.