KR102652975B1 - Novel Organo-Indium Compounds and Method for deposition of thin film using the same - Google Patents

Abstract

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

Description

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

The present invention relates to an organic indium compound and a method of manufacturing a thin film using the same. More specifically, it relates to a novel organic indium compound and a method of manufacturing a thin film using the same for forming an indium-containing thin film.

Indium is useful in the field of indium coating through electroplating due to its excellent resistance to wear and low resistance when contacting aluminum wires, and is used in the interior of sodium vapor lamps in Europe. Indium oxide is also used as a coating material.

In addition, indium oxide (In ₂ O ₃ ) is a semiconductor material used to implement ultra-high field of view, high frame rate, and large-area 3D display technology. Generally, the field effect mobility of indium oxide (In ₂ O ₃ ) is It can be used as a high-mobility thin-film transistor (TFT) of 20 to 30 cm ² /Vs, and the large overlap of indium's 5s orbitals provides an electron movement path, so it can be useful as an n-type semiconductor. The binary indium oxide (In ₂ O ₃ ) layer has the potential to be used as an optically transparent material due to its excellent electronic conduction properties and wide band gap (3.6 to 3.8 eV).

As a precursor that has been used for this indium oxide deposition, indium halide-based materials, such as indium trichloride (InCl ₃ ), have been used conventionally. However, this requires a high deposition temperature (400 to 500°C) during thin film deposition and is subject to oxidation from the outside. It has the disadvantage of requiring an oxygen source for indium, and the HCl produced as a by-product can cause damage to the thin film and internal contamination.

In addition, when using trialkyl indium-based (Me ₃ In or Et ₃ In, etc.), trialkyl indium(III) has good volatility, but has the disadvantage of being very sensitive to oxygen and moisture, and indium alkoxide-based ([In(OC ₂ H ₄ OMe) ₃ ] _m , [In(OC ₂ H ₄ NMe ₂ ) ₃ ] _m , etc.) are known to have weak volatility and are unstable in air, making their use difficult.

As a prior art regarding indium precursors in this regard, Korean Patent Publication No. 10-2021-0041843 (April 16, 2021) describes a technology regarding a precursor compound containing a ligand with a structure in which nitrogen and oxygen atoms are coordinated to indium. In addition, in Korean Patent Publication No. 10-2017-0055268 (2017.05.19), it has a main chain structure of oxygen atom-carbon atom-nitrogen atom-oxygen atom, and the two oxygen atoms are each coordinated to indium. A technology related to a precursor compound containing a ligand is described, and in Korean Patent Publication No. 10-2018-0085764 (2018.07.27), an indium-containing thin film is prepared using an indium precursor compound containing a trialkyl ligand. A manufacturing method is disclosed.

Meanwhile, in order to manufacture a thin film using a vacuum process, the precursor must generally have high volatility, and in order to manufacture nanomaterials using a solution process, the precursor must be stable in air, have appropriate solubility in the solvent, and be easy to handle. In the case of conventionally known indium compounds, there are problems such as insufficient volatility required in the vacuum process, halogen contamination occurring in the manufactured film, and inability to decompose at a stable and appropriate temperature in air required for the solution process. .

Therefore, in the formation of oxide semiconductor functional layers, there is a constant need to develop new indium precursors that have high volatility at low temperatures, do not generate halogen elements as by-products, have excellent volatility at temperatures lower than 600 °C, and have a high growth rate of thin films. It is happening.

In addition, since the indium precursors described in the prior literature contain only the indium component within the complex molecule, in order to manufacture an indium nitride thin film using them, a separate nitrogen source such as ammonia gas must be introduced in addition to the indium precursor. Stability cannot be secured during the reaction between the indium precursor and ammonia, making it difficult to apply to the mass production process through mass synthesis.

Therefore, when used to form the indium nitride thin film, by including a nitrogen (N) source in the organic indium precursor, a separate nitrogen source such as ammonia gas can not be used when forming the thin film, and the thin film can be easily formed at a low temperature. There is a continuous need for the development of new organic indium compounds that are capable of this and have improved thermal stability, volatility, and deposition rate, as well as a manufacturing process for thin films with improved physical properties using the same .

Korea Patent Publication No. 10-2021-0041843 (2021.04.16.) Korean Patent Publication No. 10-2017-0055268 (May 19, 2017) Korean Patent Publication No. 10-2018-0085764 (2018.07.27)

The present invention is intended to solve the above problems, and its first technical task is to provide a novel organic indium compound that has improved thermal stability and volatility and allows for the easy production of high-quality indium-containing thin films at low temperatures.

In addition, another object of the present invention is to provide a novel method for producing the organic indium compound, and also to provide a method for producing an indium-containing thin film using the organic indium compound.

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

[Formula A]

[Formula B]

In Formula A and Formula B above,

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 hydrogen, deuterium, 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,

R ₂₁ to R ₂₄ are Each is the same or different and independently of each other, a C ₁ -C ₁₀ linear, branched or cyclic alkyl group; C ₁ -C ₁₀ linear, branched or cyclic halogenated alkyl group; C ₆ -C ₂₀ aryl group; and C ₂ -C ₂₀ heteroaryl group; One of them is selected from among.

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, and in this case, 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 ( It may be any one selected from CH ₃ ) ₃ .

In one embodiment, m and n may each be 1 or 2, in which case, in Formula A, R ₂ to R ₇ , R ₁₂ to R ₁₇ may be the same or different and independently from each other, and may be hydrogen or deuterium. In Formula B, R ₂ to R ₇ may be the same or different and independently from each other, as hydrogen or deuterium.

In one embodiment, in Formula A, the two cyclic amine ligands coordinated to indium may be identical to each other.

In one embodiment, R ₂₁ to R ₂₄ are linear, branched or cyclic alkyl groups, each the same or different and independently of one another, C ₁ -C ₆ ; or a C ₁ -C ₆ linear, branched or cyclic halogenated alkyl group; It may be any one selected from among.

In one embodiment, in Formula B, one of R ₂ and R ₃ is hydrogen or deuterium, and the other is hydrogen, deuterium, a C ₁ -C ₆ linear, branched or cyclic alkyl group, and C ₁ - C ₆ linear, branched or cyclic halogenated alkyl group; It may be any one selected from among.

Additionally, the present invention provides a method for producing an indium-containing thin film using the organic indium compound as a precursor.

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

In addition, the present invention relates to an indium compound represented by the following compound B1; An indium compound represented by compound B2 below; A nitrogen-containing ring compound represented by the following compound C1; and a nitrogen-containing ring compound represented by compound C2; A method of producing an organic indium compound represented by Formula A is provided using each as a reactant.

[Compound B1] [Compound B2]

In(X ₁ )(R ₂₁ )(R ₂₂ ) In(X ₂ )(R ₂₃ )(R ₂₄ )

[Compound C1] [Compound C2]

[Formula A]

In the compound B1 and compound B2,

_{Wherein X 1 to ​ ​ ​ ​} Or any one selected from cyclic alkylsilyl group and C ₆ -C ₁₈ arylsilyl group,

In Compound B1, Compound B2, Compound C1, Compound C2 and Formula A, R ₁ to R ₇ , R ₁₁ to R ₁₇ , R ₂₁ to R ₂₄ , m and n are each as previously defined.

In addition, the present invention relates to an indium compound represented by the following compound B1; and a nitrogen-containing ring compound represented by the following compound C1; Provided is a method for producing an organic indium compound represented by Formula B using each as a reactant.

[Compound B1]

In(X ₁ )(R ₂₁ )(R ₂₂ )

[Compound C1]

[Formula B]

In the compound B1,

_{Wherein ​ ​ ​ ​ ​ ​ ​ ​} Any one selected from arylsilyl groups,

R ₁ to R ₇ , R ₂₁ to R ₂₂ and m in Compound B1, Compound C1 and Formula B are each as previously defined.

Since the organic indium compound according to the present invention has the effect of improving thermal stability and volatility when forming an indium-containing thin film, a large-area and highly uniform indium-containing thin film can be easily and stably manufactured using it.

In addition, when the organic indium precursor according to the present invention is used to form an indium nitride thin film, it contains a nitrogen (N) source in the organic indium precursor, so that the organic indium precursor according to the present invention has a low temperature without using a separate nitrogen source such as ammonia gas when forming the thin film. It can have the advantage of being able to easily form a thin film at any temperature.

Figure 1 is a diagram showing the X-ray single crystal structure of an indium precursor prepared according to Synthesis Example 1.
Figure 2 is a diagram showing the results of thermogravimetric analysis (TGA) of the indium precursor prepared according to Synthesis Examples 1 to 4.

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 indium-containing thin film can be produced when using an indium compound in which a nitrogen-containing organic ligand having a specific structural formula is coordinated to indium. was able to complete.

Hereinafter, the organic indium compound according to the present invention, its manufacturing method, and the manufacturing method of an indium-containing thin film using the same will be described in more detail.

The present invention provides an organic indium compound represented by the following [Formula A] or [Formula B].

[Formula A]

[Formula B]

In Formula A and Formula B above,

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 hydrogen, deuterium, 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,

R ₂₁ to R ₂₄ are Each is the same or different and independently of each other, a C ₁ -C ₁₀ linear, branched or cyclic alkyl group; C ₁ -C ₁₀ linear, branched or cyclic halogenated alkyl group; C ₆ -C ₂₀ aryl group; and C ₂ -C ₂₀ heteroaryl group; It is one selected from among.

The compound represented by the formula A according to the present invention corresponds to an organic indium complex of a dimeric structure in which two cyclic amine ligands containing two nitrogen atoms are each coordinated to two indium atoms, and also, according to the present invention, The compound represented by the formula B corresponds to an organic indium complex in which one cyclic amine ligand containing two nitrogen atoms is coordinated to the central indium atom, and is represented by the [Formula A] or [Formula B] according to the present invention. The indicated organic tin complex can have excellent chemical-thermal stability when used as a precursor to form thin films for chemical vapor deposition, atomic layer deposition, or solution processing, producing high-quality, large-area, and highly uniform indium-containing thin films. can be provided.

Here, the cyclic amine ligand coordinated to the central indium atom in the organic indium compound represented by [Formula A] of the present invention is a nitrogen atom bonded to R1 through a dehydrogenation reaction from each of Compound C1 and Compound C2 below. When hydrogen is removed or the hydrogen of the nitrogen atom bonded to R11 is removed, it can coordinate with indium as a ligand.

[Compound C1] [Compound C2]

In addition, the cyclic amine ligand coordinated to the central indium atom in the organic indium compound represented by [Formula B] of the present invention is a dehydrogenation reaction from the compound C1, whereby the hydrogen of the nitrogen atom bonded to R1 is released, thereby forming a ligand. It can act as.

In addition, in the organic indium compound according to the present invention, R ₂ to R ₇ , which are substituents in the cyclic amine ligand derived from the compound C1 and compound C2 in [Formula A] and [Formula B], R ₁₂ to R ₁₇ are preferably 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 It is preferable, and in this case, it has excellent chemical-thermal stability and can have a fast deposition rate of a thin film even at a relatively low temperature.

In addition, in the organic indium compound according to the present invention, the substituents R ₁ and R ₁₁ are preferably 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 preferable that it is any one selected from among _{the three} , and through this, it has excellent chemical-thermal stability and can have the property of fast deposition of a thin film even at a relatively low temperature.

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

In addition, as a more preferred embodiment of the present invention, when m and n are preferably each 1 or 2, in Formula A, R ₂ to R ₇ R ₁₂ to R ₁₇ may be the same or different and independently from each other, and may be hydrogen or deuterium. In Formula B, R ₂ to R ₇ may be the same or different and independently from each other, as hydrogen or deuterium.

In addition, as a more preferred embodiment of the present invention, in Formula A, each cyclic amine ligand derived from Compound C1 and Compound C2 in [Formula A], which is coordinated to the indium, may be identical to each other, , In this case, the manufacturing process of the indium complex is simple and the ligand coordinated to indium is the same, so 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. .

In addition, in one embodiment of the present invention, R ₂₁ to R ₂₄ in [Formula A] and [Formula B] are Preferably each is the same or different and independently of each other, C ₁ -C ₆ linear, branched or cyclic alkyl groups; or a C ₁ -C ₆ linear, branched or cyclic halogenated alkyl group; It may be any one selected from among, and more preferably, R ₂₁ to R ₂₄ are Each may be the same or different and may be any one selected from CH ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ , in which case It has excellent chemical-thermal stability and can have a fast deposition rate of thin films even at relatively low temperatures.

In addition, as a more preferred embodiment of the present invention, in Formula B, one of R ₂ and R ₃ is hydrogen or deuterium, and the other is hydrogen, deuterium, C ₁ -C ₆ linear, branched or cyclic alkyl groups and C ₁ -C ₆ linear, branched or cyclic halogenated alkyl groups; It may be any one selected from among.

Meanwhile, the present invention can provide a method for producing an indium-containing thin film, preferably an indium oxide thin film or an indium nitride thin film, using the organic indium compound represented by Formula A or Formula B as a precursor. In this case, The process of growing an indium-containing thin film can be performed by chemical vapor deposition (CVD), atomic layer deposition (ALD), or a solution process.

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 An indium-containing thin film with a thickness and density of can be manufactured.

More specifically, when using the chemical vapor deposition (CVD) method, the reactant containing the organic indium precursor of the present invention is supplied in a gaseous state to a reactor containing a substrate of various types or shapes, thereby containing indium on the substrate. A thin film can be formed. In this case, the indium compound represented by Formula A or Formula B of the present invention is thermally stable and has good volatility, so an indium-containing 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 indium 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.

In addition, in the present invention, when forming a thin film by the solution process, an organic indium compound (precursor) is dissolved in a solvent, coated on the substrate, and then heated or energy is applied from the outside to form an indium-containing thin film on the substrate. At this time, a high-quality thin film can be formed by selecting an appropriate solvent and controlling the heating conditions for thin film formation.

Meanwhile, the organic indium compound represented by Formula A or Formula B according to the present invention contains a total of 2 or 4 nitrogen atoms in a cyclic amine ligand coordinated to an indium atom in the complex, so that when forming an indium nitride thin film, It can have the additional advantage of being able to easily form an indium nitride thin film without adding additional nitrogen components such as ammonia gas.

Meanwhile, the present invention relates to an indium compound represented by the following compound B1; An indium compound represented by compound B2 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 B1] [Compound B2]

In(X ₁ )(R ₂₁ )(R ₂₂ ) In(X ₂ )(R ₂₃ )(R ₂₄ )

[Compound C1] [Compound C2]

[Formula A]

In the compound B1 and compound B2,

_{Wherein X 1 to ​ ​ ​ ​} Or any one selected from cyclic alkylsilyl group and C ₆ -C ₁₈ arylsilyl group,

In Compound B1, Compound B2, Compound C1, Compound C2 and Formula A, R ₁ to R ₇ , R ₁₁ to R ₁₇ , R ₂₁ to R ₂₄ , m and n are each as previously defined.

That is, the organic indium compound represented by formula A of the present invention is a compound represented by compound C1 instead of the X ₁ ligand in the indium compound represented by compound B1 and the X ₁ ligand in the indium compound represented by compound B2. ; and a compound represented by compound C2; are used as reactants, respectively, by coordinating two nitrogen-containing heterocyclic ligands (cyclic amine ligands) derived from compound C1 and compound C2 to indium atoms, to the above [Formula A] The indicated organic indium compounds can be produced.

Here, the substituents R ₂ to R ₇ in the compounds C1 and C2, R ₁₂ to R ₁₇ are preferably 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, and more preferably, any one selected from hydrogen, deuterium, CH ₃ , C ₂ H ₅ , CH(CH ₃ ) ₂ and C(CH ₃ ) ₃ .

In addition, R ₁ and R ₁₁ in the compounds C1 and C2 are preferably 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 compounds C1 and C2 are preferably the same or different, and may be independently 1 or 2.

In addition, the present invention relates to an indium compound represented by the following compound B1; and a nitrogen-containing ring compound represented by the following compound C1; are used as reactants, respectively, to produce an organic indium compound represented by the formula B. A method for producing an organic indium compound represented by the formula B is provided.

[Compound B1]

In(X ₁ )(R ₂₁ )(R ₂₂ )

[Compound C1]

[Formula B]

In the compound B1,

_{Wherein ​ ​ ​ ​ ​ ​ ​ ​} Any one selected from arylsilyl groups,

R ₁ to R ₇ , R ₂₁ to R ₂₂ and m in Compound B1, Compound C1 and Formula B are each as previously defined.

That is, the organic indium compound represented by Chemical Formula B of the present invention uses the compound represented by Compound C1 as a reactant instead of _the By coordinating a heterocyclic ligand (cyclic amine ligand) to an indium atom, the organic indium compound represented by the above [Formula B] can be produced.

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

In addition, R ₁ in the compound C1 is preferably 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; Any one selected from among may be used, and more preferably, R ₁ may be any one selected from CH ₃ , C ₂ H ₅ , CH(CH ₃ ) ₂ and C(CH ₃ ) ₃ .

In addition, in the formula C1, m may preferably be 1 or 2.

Here, when an organic solvent is used in producing the organic indium compound represented by Formula A or Formula B, suitable types of organic solvents include hexane, toluene, tetrahydrofuran, hexane, cyclohexane, diethyl ether, etc. Examples include, but are not limited to, hexane, toluene, or cyclohexane.

The reaction conditions for producing the organic indium compound represented by the formula A or formula B are preferably in the organic solvent, mixing each reactant, and reacting at a temperature in the range of 0 to 150°C, preferably 10 to 70°C. The reaction can proceed through stirring for 1 hour to 3 days, and through this, the organic indium compound represented by Formula A or Formula B can be produced.

At this time, when producing an organic indium compound represented by Formula A or Formula B, in order to separate the product from by-products or unreacted products generated during the reaction, recrystallization, sublimation, distillation, extraction ( A novel organic indium compound of high purity can be obtained by separation using extraction or column chromatography.

The high-purity organic indium compound represented by Formula A or Formula B 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.

Example 1 (Preparation of an organic indium compound represented by [Formula A])

[Scheme 1]

Synthesis Example 1: [In(tbip)(Me) ₂ ] ₂ Manufacture of (tbip: tert-butyl-iminopyrrolidinate)

A solution of tbipH (0.50g, 3.56 mmol, 1.0 equiv) dissolved in 10 mL of hexane was slowly added to a solution of In(Me) ₃ (0.57g, 3.56 mmol, 1.0 equiv) dissolved in 20 mL of hexane at room temperature and then placed in an argon atmosphere. After stirring for 24 hours under reduced pressure, the reaction solvent was removed. The mixture was recrystallized in hexane at room temperature to obtain transparent crystals (1.203 g, yield 59.4%).

¹ H NMR (400 MHz, Benzene- d ₆ ) δ (ppm): 3.16 (t, J = 6.8 Hz, 2H), 2.03 (t, J = 7.9 Hz, 2H), 1.64 (p, J = 7.2 Hz, 2H), 1.10 (s, 9H), 0.12 (s, 6H).

¹³ C NMR (101 MHz, Benzene- d ₆ ) δ(ppm): 177.87, 50.53, 48.66, 31.77, 29.77, 25.75, -6.33.

Anal. Calcd for C ₂₀ H ₄₂ In ₂ N ₄ : C, 42.28; H, 7.45; N, 9.86. Found: C, 41.93; H, 7.53; N, 9.71.

Example 2 (Preparation of an organic indium compound represented by [Formula B])

[Scheme 2]

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

A solution of tbmpH (0.308g, 2.00 mmol, 1.0 equiv) dissolved in 5 mL of hexane was slowly added to a solution of In(Me) ₃ (0.320g, 2.00 mmol, 1.0 equiv) dissolved in 30 mL of hexane at room temperature, and then added with argon. After stirring under atmospheric air for 24 hours, the reaction solvent was removed under reduced pressure. The obtained mixture was distilled under reduced pressure (55 °C/0.8 torr) to obtain a colorless liquid (0.400 g, yield 67%).

¹ H NMR (400 MHz, Benzene- d ₆ ) δ (ppm): 3.53 (h, J = 6.3 Hz, 1H), 2.20 (ddd, J = 16.1, 9.2, 5.0 Hz, 1H), 2.05 (ddd, J = 16.2, 9.2, 7.6 Hz, 1H), 1.88 - 1.82 (m, 1H), 1.30 - 1.25 (m, 1H), 1.09 (s, 9H), 0.97 (d, J = 6.3 Hz, 3H), 0.13 ( s, 6H).

¹³ C NMR (101 MHz, Benzene- d ₆ ) δ(ppm): 177.29, 55.73, 50.89, 34.02, 32.17, 30.48, 23.81, -5.84.

Anal. Calcd for C ₁₁ H ₂₃ InN ₂ : C, 44.32; H, 7.78; N, 9.40. Found: C, 44.55; H, 7.87; N, 9.36.

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

A solution of tbtH (0.310 g, 2.00 mmol, 1.0 equiv) dissolved in 5 mL of hexane was slowly added to a solution of In(Me) ₃ (0.321 g, 2.00 mmol, 1.0 equiv) dissolved in 30 mL of hexane at room temperature, and then added with argon. After stirring under atmospheric air for 24 hours, the reaction solvent was removed under reduced pressure. The obtained mixture was distilled under reduced pressure (70° C/0.4 torr) to obtain a colorless liquid (0.477 g, yield 80%).

¹ H NMR (400 MHz, Benzene- d ₆ ) δ (ppm): 3.13 (td, J = 5.0, 3.9, 1.9 Hz, 2H), 2.09 (p, J = 3.6 Hz, 2H), 1.29 (p, J = 3.0 Hz, 4H), 1.11 (s, 9H), 0.11 (s, 6H).

¹³ C NMR (101 MHz, Benzene- d ₆ ) δ(ppm): 169.68, 50.48, 45.66, 32.49, 28.24, 24.04, 20.63, -6.41.

Anal. Calcd for C ₁₁ H ₂₃ InN ₂ : C, 44.32; H, 7.78; N, 9.40. Found: C, 44.29; H, 7.87; N, 9.38.

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

A solution of tbtaH (0.526 g, 3.12 mmol, 1.0 equiv) dissolved in 5 mL toluene was slowly added to a solution of In(Me) ₃ (0.500 g, 3.12 mmol, 1.0 equiv) dissolved in 30 mL of toluene at room temperature, and then added with argon. After stirring under atmospheric air for 24 hours, the reaction solvent was removed under reduced pressure. The obtained mixture was distilled under reduced pressure (75 °C/0.6 torr) to obtain a colorless liquid (0.588 g, yield 60%).

¹ H NMR (400 MHz, Benzene- d ₆ ) δ (ppm): 3.04 - 2.98 (m, 2H), 2.23 - 2.16 (m, 2H), 1.46 (p, J = 5.8 Hz, 2H), 1.35 (p , J = 5.8, 5.1 Hz, 4H), 1.12 (s, 9H), 0.07 (s, 6H).

¹³ C NMR (101 MHz, Benzene- d ₆ ) δ(ppm): 177.01, 50.46, 47.53, 32.80, 31.42, 31.26, 30.14, 24.94, -6.34.

Experimental Example 1: X-ray single crystal structure analysis

In order to confirm the structure of the solid phase of the indium precursor compound synthesized in Synthesis Example 1, the single crystal structure was confirmed using a Bruker SMART APEX II It was confirmed that the indium precursor compound had a dimeric structure.

Experimental Example 1: Thermogravimetric Analysis (TGA)

To measure the thermal stability, volatility, and thermal decomposition temperature of the organoindium complexes synthesized in Synthesis Examples 1 to 4, thermogravimetric analysis was performed while heating to 600°C at a rate of 5°C per minute using TGA/DSC1 from Mettler-Toledo. analysis (TGA) was performed, and the results are shown in Figure 2.

As shown in FIG. 2, a mass reduction of more than 48% was observed for [In(Me) ₂ (tbip)] ₂ in Synthesis Example 1 at 75°C, and an additional 11% mass reduction was observed at 200°C. . For In(Me) ₂ (tbmp) in Synthesis Example 2, a mass reduction of more than 52% was observed at 75°C, and an additional mass reduction of 7% was observed at 225°C. For In(Me) ₂ (tbtp) in Synthesis Example 3, a 56% mass reduction was observed at 75°C, and an additional mass reduction of 21% was observed at 225°C. It was confirmed that 35% of the remaining mass remained at the final temperature of 525°C. In addition, a mass reduction of more than 53% was observed for In(Me) ₂ (tbta) in Synthesis Example 4 at 50°C, and an additional mass reduction of 9% was observed at 250°C.

The TGA analysis results and FIG. 2 show that the indium precursor compound obtained according to the present invention has excellent properties for forming an indium-containing 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 (13)

An organic indium compound represented by the following [Chemical Formula B].
[Formula B]

In Formula B,
R ₂ to R ₇ 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 is hydrogen, deuterium, C ₁ -C ₁₀ linear, branched or cyclic alkyl group; and a C ₁ -C ₁₀ linear, branched or cyclic halogenated alkyl group,
where m is any integer selected from 1 to 3,
When m is 2 or more, each ' ' is the same or different,
The R ₂₁ to R ₂₂ are Each is the same or different and independently of each other, a C ₁ -C ₁₀ linear, branched or cyclic alkyl group; C ₁ -C ₁₀ linear, branched or cyclic halogenated alkyl group; and C ₆ -C ₂₀ aryl group; One of them is selected from among.
According to paragraph 1,
Wherein R ₂ to R ₇ are the same or different and are independently selected from hydrogen, deuterium, CH ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ An organic indium compound.
According to paragraph 1,
R ₁ is 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; An organic indium compound selected from the group consisting of:
According to paragraph 3,
The R ₁ is an organic indium compound selected from CH ₃ , C ₂ H ₅ , CH(CH ₃ ) ₂ and C(CH ₃ ) ₃ .
According to paragraph 1,
An organic indium compound wherein m is 1 or 2.
According to clause 5,
In Formula B,
The organic indium compound wherein R ₂ to R ₇ are the same or different and independently of each other, hydrogen or deuterium.
delete According to paragraph 1,
The R ₂₁ to R ₂₂ are linear, branched or cyclic alkyl groups, each the same or different and independently of one another, C ₁ -C ₆ ; or a C ₁ -C ₆ linear, branched or cyclic halogenated alkyl group; An organic indium compound selected from the group consisting of:
According to paragraph 1,
In Formula B,
One of R ₂ and R ₃ is hydrogen or deuterium,
the other is hydrogen, deuterium, a C ₁ -C ₆ linear, branched or cyclic alkyl group and a C ₁ -C ₆ linear, branched or cyclic halogenated alkyl group; An organic indium compound selected from the group consisting of:
A method of producing an indium-containing thin film using the organic indium compound according to any one of claims 1 to 6, 8, and 9 as a precursor.
According to clause 10,
A method of manufacturing an indium nitride thin film, characterized in that the process of manufacturing the indium-containing thin film is performed by chemical vapor deposition (CVD), atomic layer deposition (ALD), or a solution process.
delete An indium compound represented by compound B1 below; and a nitrogen-containing ring compound represented by the following compound C1; A method for producing an organic indium compound represented by the formula B of claim 1, characterized in that the organic indium compound represented by the formula B is prepared by using each as a reactant.
[Compound B1]
In(X ₁ )(R ₂₁ )(R ₂₂ )
[Compound C1]

[Formula B]

In the compound B1,
_{Wherein ​ ​ ​ ​ ​ ​ ​ ​} Any one selected from arylsilyl groups,
R ₁ to R ₇ , R ₂₁ to R ₂₂ and m in Compound B1, Compound C1 and Formula B are each as defined in paragraph 1 above.