WO2024090836A1

WO2024090836A1 - Gallium compound, thin film deposition composition containing same, and method for producing thin film using same

Info

Publication number: WO2024090836A1
Application number: PCT/KR2023/015314
Authority: WO
Inventors: 이경은; 박주호; 박희권; 김소연; 양택승; 송창호; 김진동
Original assignee: 주식회사 레이크머티리얼즈
Priority date: 2022-10-27
Filing date: 2023-10-05
Publication date: 2024-05-02

Abstract

The present invention pertains to: a gallium compound; a method for producing same; a thin film deposition composition containing same; and a method for producing a thin film using same. The gallium compound of the present invention has excellent volatility and stability, thus being very useful as a precursor for a gallium-containing thin film, and has excellent adsorption to a substrate, thus making it possible to produce a higher quality gallium-containing thin film.

Description

Gallium compound, composition for thin film deposition containing the same, and method for producing a thin film using the same

The present invention relates to a gallium compound, a method for producing the same, a composition for thin film deposition containing the same, and a method for producing a thin film using the same. More specifically, a gallium compound useful as a precursor for depositing a gallium-containing thin film, a method for producing the same, and a composition containing the same. It relates to a composition for depositing a gallium-containing thin film and a method of manufacturing a gallium-containing thin film using the same.

The development of new technologies and materials in the semiconductor industry has made possible miniaturization, high reliability, high speed, high functionality, and high integration of devices such as semiconductor integrated circuits. Accordingly, the properties required for precursors to form thin films have also changed. In general, the characteristics required for a thin film deposition precursor are a gas or liquid compound with high vapor pressure, excellent thermal stability, and easy transfer to the deposition chamber, and furthermore, reactivity with the reaction gases used depending on the type of thin film being manufactured. must also be excellent.

In addition, thin film formation methods used in the manufacture of semiconductor devices include physical vapor growth method (PVD method) and chemical vapor growth method (CVD method) by sputtering. However, in the next generation of semiconductor manufacturing, a uniform thin film is required even on the surface of a complex three-dimensional structure of a miniaturized device, so the PVD method is not suitable because it is difficult to form a uniform film on the uneven surface.

Accordingly, as a method of forming a thin film with excellent step coverage, a CVD method in which raw materials are transferred to a reaction tank as a gas and decomposed to form a film, or an atomic layer deposition (ALD) method in which raw materials adsorbed on the substrate surface are decomposed and a film is deposited ) Thin film formation method has been reviewed and is mainly used.

Meanwhile, precursors containing Group 13 metals have excellent stability and conductivity, and are attracting attention as precursors for thin film deposition. In particular, group 13 metal oxides can be used as transparent oxide semiconductor materials and can be applied as electrodes, conductive coating materials, etc.

Gallium oxide (Ga ₂ O ₃ ), which contains gallium among Group 13 metals, has a wide band gap energy and is used in display fields such as gas sensors and transparent conductors, as well as next-generation solar cells, specifically phosphor raw materials, semiconductors, and CIGS (copper). indium gallium selenide) It is used as a material applicable to solar cells, ultra-thin liquid crystal displays (TFT-LCD), and organic light-emitting diodes (OLED). In addition, gallium oxide is an electrical insulator at room temperature and a semiconductor at temperatures above 500°C, having a chemically and thermally stable monoclinic form.

Trimethylgallium (TMG) is the most widely used gallium precursor, but it is very sensitive to air and ignites spontaneously when exposed, making it difficult to handle. In addition, gallium complexes such as [Ga(hfac)]3 (hfac = hexafluoroacetylacetonate) and [Ga(OCH(CF3)2)3(HNMe2)] have been reported, but they contain halogen elements, especially fluorine, so they are difficult to deposit when depositing thin films. Gallium fluoride (GaF) is formed due to fluorine, causing contamination in the thin film, which can cause serious deterioration of device characteristics and reliability problems during the semiconductor device process. In addition, gallium alkoxide dimers or tetramers were reported, but they did not correspond to a single monomer and had low volatility to be used as a precursor for thin film deposition.

Precursors for thin film deposition necessarily require high volatility and thermal stability, but previously reported gallium compounds have insufficient volatility to be used as precursors or have problems of contaminating thin films with halogen elements, including halogen elements. .

Therefore, it is less reactive in moisture or air, so there is no risk of spontaneous combustion and is easy to handle. The compound itself does not contain halogen elements such as fluorine, but contains gallium that can be applied to ALD and CVD processes with high volatility and thermal stability. There is a need for the development of precursors for thin film deposition.

The present invention provides a gallium compound that has improved volatility and thermal stability and is very useful for producing high-quality gallium-containing thin films, and a method for producing the same.

Additionally, the present invention provides a composition for depositing a gallium-containing thin film containing the gallium compound of the present invention.

Additionally, the present invention provides a method for producing a gallium-containing thin film using the gallium compound or the composition for depositing a gallium-containing thin film of the present invention.

One aspect of the present invention is to provide a gallium compound that is very useful as a precursor for gallium-containing thin films due to its excellent volatility and stability. The gallium compound of the present invention is represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ is C1-C10 alkyl;

R ² is C1-C10 alkyl, -OR' or -SR';

R' is C1-C10 alkyl or C2-C10 alkenyl;

X ¹ is O or S;

R ^a and R ^b are independently hydrogen or C1-C10 alkyl;

The alkenyl of R' may be further substituted with one or more C1-C10 alkyl.

Another aspect of the present invention is to provide a method for producing the gallium compound. The method for producing the gallium compound of the present invention is to react a trialkyl gallium compound of the following formula (3) and an allyl compound of the formula (4) to obtain a compound of the formula (1-1): It includes; manufacturing a gallium compound.

[Formula 1-1]

[Formula 3]

[Formula 4]

In Formulas 1-1, 3 and 4,

R ¹ , R ^2a and R ^3a are each independently C1-C10 alkyl;

R ^2b is C1-C10 alkyl or

ego;

X ¹ is O or S;

R ^a and R ^b are independently hydrogen or C1-C10 alkyl.

Another aspect of the present invention provides a composition for depositing a gallium-containing thin film containing a gallium compound represented by Formula 1 according to an embodiment, and a method of forming a gallium-containing thin film using the same.

Another aspect of the present invention provides a method of forming a gallium-containing thin film using a gallium compound represented by Formula 1 according to an embodiment.

The gallium compound of the present invention has good thermal stability, high volatility, and excellent cohesiveness, so it is useful as a precursor for gallium-containing thin films. Furthermore, it has excellent adsorption with a substrate, making it possible to produce higher quality gallium-containing thin films. In addition, the gallium compound of the present invention exists in a liquid state at room temperature and a manageable pressure, making it easy to handle. In addition, since the gallium compound of the present invention exists in a liquid state at room temperature, it is supplied at a uniform concentration to a large-area substrate and has excellent thin film thickness uniformity. In addition, the gallium compound of the present invention does not decompose even during high processing temperatures and is stored. Stability is excellent.

In addition, when manufacturing a gallium-containing thin film using the gallium compound of the present invention or a composition for thin film deposition containing the gallium compound, it is possible to produce a uniform thin film with high density and high purity due to excellent cohesion at a high deposition rate.

In addition, the method for manufacturing a gallium-containing thin film of the present invention enables the production of a high-quality gallium-containing thin film with excellent thermal stability and durability by manufacturing a gallium-containing thin film using the gallium compound or a composition for gallium-containing thin film deposition containing the gallium compound. .

Figure 1 - TGA analysis results of gallium compound 1 prepared in Example 1

Figure 2 - TGA analysis results of gallium compound 2 prepared in Example 2

Figure 3 - Growth rate per cycle of gallium-containing thin films as a function of injection time of gallium compound 1.

Figure 4 - XPS analysis results of gallium-containing thin film prepared in Example 8

Figure 5 - Error analysis results of IGZO thin films prepared in Example 11 and Comparative Example 2

Figure 6 - Error analysis results of IGZO thin films prepared in Example 11 and Comparative Example 2

Hereinafter, the present invention will be described in more detail. Unless otherwise defined, the technical and scientific terms used herein have meanings commonly understood by those skilled in the art to which this invention pertains, and the following description will not unnecessarily obscure the gist of the present invention. Descriptions of possible notification functions and configurations are omitted.

As used herein, the singular forms “a,” “an,” and “the” are intended to also include the plural forms, unless the context clearly dictates otherwise.

As used herein, “comprises” is an open description that has the equivalent meaning to expressions such as “comprises,” “contains,” “has,” or “characterized by” elements that are not additionally listed; Does not exclude materials or processes.

As used herein, the term “gallium compound” may be represented by Chemical Formula 1 and has an equivalent meaning to expressions such as “gallium precursor” or “gallium precursor compound.”

As used herein, the term “thermal stability” may mean that physical properties do not change even during a continuous heating process or a high temperature process, and specifically means that no structural change occurs even when exposed to the harsh conditions described above for a long period of time. .

As used herein, “alkyl” refers to a saturated straight-chain or branched non-cyclic hydrocarbon having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. “Lower alkyl” means straight-chain or branched alkyl having 1 to 4 carbon atoms. Representative saturated straight-chain alkyls include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl, while saturated branched alkyls include Alkyl is isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3 -Methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,3-dimethylbutyl, 2,3- Dimethylpentyl, 2,4-dimethylpentyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 2,2-dimethylpentyl, 2,2-dimethylhexyl, 3,3-dimethyl Pentyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 2-ethylpentyl, 3-ethylpentyl, 2-dethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methyl-2-ethylpentyl, 2-methyl-3-ethylpentyl, 2-methyl-4-ethylpentyl, 2-methyl-2-ethylhexyl, 2-methyl-3-ethylhexyl, 2-methyl-4-ethylhexyl, 2,2-di Includes ethylpentyl, 3,3-diethylhexyl, 2,2-diethylhexyl, and 3,3-diethylhexyl.

When written as “C1-C10” in this specification, it means that the number of carbon atoms is 1 to 10. For example, C1-C4alkyl refers to alkyl having 1 to 4 carbon atoms. Specific examples may be methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, or tert-butyl. .

As used herein, “alkenyl” refers to a saturated straight-chain or branched group containing 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms and at least one carbon-carbon double bond. refers to terrestrial non-cyclic hydrocarbons. Representative straight-chain and branched (C2-C10) alkenyls include vinyl, allyl, 1-butenyl, 2-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl, 2,3-dimethyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1-heptenyl, 2-heptenyl, 3- Heptenyl, 1-octenyl, 2-octenyl, 3-octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 2-decenyl, and 3-decenyl Includes. These alkenyl groups may be optionally substituted.

One aspect of the present invention is to provide a gallium compound that can be very useful as a precursor for a gallium-containing thin film. The gallium compound of the present invention is represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ is C1-C10 alkyl;

R ² is C1-C10 alkyl, -OR' or -SR';

R' is C1-C10 alkyl or C2-C10 alkenyl;

X ¹ is O or S;

R ^a and R ^b are independently hydrogen or C1-C10 alkyl;

The alkenyl of R' may be further substituted with one or more C1-C10 alkyl.

In Formula 1 according to one embodiment, R ¹ is C1-C10 alkyl; R ² is C1-C10 alkyl, -OR' or -SR';R' is C1-C10 alkyl or allyl; X ¹ is O or S; R ^a and R ^b are independently hydrogen or C1-C10 alkyl; Allyl of R' may be further substituted with one or more C1-C10 alkyl. Preferably, in Formula 1 according to one embodiment, R ¹ is C1-C6 alkyl; R ² is C1-C6alkyl or -OR';R' is C1-C6alkyl or allyl; X ¹ is O; R ^a and R ^b are independently hydrogen or C1-C6alkyl; Allyl of R' may be further substituted with one or more C1-C6alkyl.

Preferably, in one embodiment, the gallium compound of Chemical Formula 1 may be represented by the following Chemical Formula 1-1.

[Formula 1-1]

In Formula 1-1,

R ¹ is C1-C10 alkyl;

R ^2b is C1-C10 alkyl or

ego;

X ¹ is O or S;

R ^a and R ^b are independently hydrogen or C1-C10 alkyl.

In Formula 1-1 according to one embodiment, R ¹ is C1-C6 alkyl; R ^2b is C1-C6alkyl or

ego; X ¹ is O; R ^a and R ^b may independently be hydrogen or C1-C6alkyl.

In terms of obtaining a high-quality transition metal-containing thin film as a precursor for transition metal-containing thin film deposition due to its high volatility and high thermal stability, the gallium compound of Formula 1 according to an embodiment may be represented by the following Formula 2.

[Formula 2]

In Formula 2,

R ¹ is C1-C4alkyl;

R ² is C1-C4alkyl or

ego;

R ^a , R ^b , R ^c and R ^d are independently hydrogen or C1-C4alkyl.

More preferably, the gallium compound of Formula 2 according to one embodiment may be represented by the following Formula 2-1 or Formula 2-2.

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2,

R ¹ is C1-C4alkyl;

R ^2'' is C1-C4alkyl;

R ^e is hydrogen or C1-C4alkyl.

In one embodiment, R ¹ is methyl or ethyl; R ^2'' is methyl or ethyl; R ^e may be hydrogen, methyl or ethyl.

Specifically, the gallium compound according to one embodiment may be selected from the following compounds, but is not limited thereto.

The gallium compound of the present invention has a structure in which at least one alkyl ligand and one allyloxy or allylthio ligand are bonded to gallium (Ga), a central metal, and the thermal stability and reactivity are significantly improved due to the introduction of a specific ligand. Due to its high volatility, high-quality thin films can be manufactured.

In addition, since the gallium compound of the present invention exists in liquid form at room temperature and pressure, it has high storage stability and excellent volatility, so it can be used as a precursor for deposition of gallium-containing thin films to produce high-density, high-purity gallium-containing thin films.

In atomic layer deposition (ALD), the reactants must be highly volatile, the material must be stable, and the reactivity must be high. Atomic layer deposition (ALD) is a method of supplying reaction raw materials separately. During one cycle of deposition, a thin film of less than a monolayer is grown through surface reaction, and the ligand of the reaction raw material adsorbed on the substrate is later It is removed through a chemical reaction with other reaction raw materials supplied to it. When heating a precursor compound as a reactant for atomic layer deposition, the liquid phase can be much more advantageous in terms of reaction speed and process than the solid phase.

[Formula 1-1]

[Formula 3]

[Formula 4]

In Formulas 1-1, 3 and 4,

R ¹ , R ^2a and R ^3a are each independently C1-C10 alkyl;

R ^2b is C1-C10 alkyl or

ego;

X ¹ is O or S;

R ^a and R ^b are independently hydrogen or C1-C10 alkyl.

For example, the gallium compound of the present invention can be manufactured by the same method as described above, but any other method is possible within the range recognized by a person skilled in the art.

Preferably, the method for producing a gallium compound according to an embodiment may include reacting a trialkyl gallium compound of Formula 3 below and an allyl alcohol compound of Formula 4-1 below to produce a gallium compound of Formula 2 below. .

[Formula 2]

[Formula 3]

[Formula 4-1]

In

Formulas

2, 3 and 4-1,

R ¹ , R ^2a and R ^3a are each independently C1-C4 alkyl;

R ^2b is C1-C4alkyl or

ego;

R ^a and R ^b are independently hydrogen or C1-C4alkyl.

In one embodiment, the allyl compound of Formula 4 may be used in an amount of 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol, per 1 mole of the trialkyl gallium compound of Formula 3.

In one embodiment, the reaction may be performed in an organic solvent, and the usable organic solvent is not limited, but an organic solvent having high solubility for the reactants may be used, specifically n-hexane. , one (single solvent) or a mixture of two or more solvents selected from chlorobenzene, toluene, dichloroethane (DCE), dioxane, diethyl ether, and dichloromethane (DCM) may be used, and more preferably, the reaction yield, etc. In terms of increasing efficiency, n-hexane, ether, or diethyl ether can be used.

In one embodiment, the reaction may be performed under an inert gas atmosphere such as nitrogen or argon, and the solution containing the trialkyl gallium compound of Formula 3 is cooled to a low temperature below 0° C. and then added to the solution of Formula 4. The reaction can be performed at 20 to 30° C. after slowly adding the allyl compound.

The method of manufacturing the gallium-containing thin film is a common method used in the industry, specifically atomic layer deposition (ALD), chemical vapor deposition (CVD), metal organic chemical vapor deposition (MOCVD), and low pressure chemical vapor deposition (LPCVD). , it may be plasma-enhanced chemical vapor deposition (PECVD) or plasma-enhanced atomic layer deposition (PEALD).

More preferably, the method for manufacturing the gallium-containing thin film according to an embodiment may be atomic layer deposition (ALD), chemical vapor deposition (CVD), or metal organic chemical vapor deposition (MOCVD).

A gallium-containing thin film according to an embodiment may be manufactured by a common method used in the art, for example, metal organic chemical vapor deposition (MOCVD), atomic layer deposition (ALD), low pressure vapor deposition (LPCVD), and plasma enhanced Examples include vapor deposition (PECVD) or plasma enhanced atomic layer deposition (PEALD), but atomic layer deposition (ALD) or plasma enhanced atomic layer deposition (PEALD) is preferred.

In one embodiment, the gallium-containing thin film of the present invention may be manufactured by atomic layer deposition (ALD).

A method of manufacturing a gallium-containing thin film according to an embodiment includes forming a thin film by depositing the gallium compound on a substrate, and specifically, a) adsorbing the gallium compound on the substrate; b) purging non-adsorbed gallium compounds; c) forming a gallium-containing thin film by injecting a reaction gas; and d) purging residual reaction gas and reaction by-products.

A method of manufacturing a gallium-containing thin film according to an embodiment may include forming a single-layer or multi-layer thin film by depositing the gallium compound and at least one selected from an indium precursor and a zinc precursor on a substrate, wherein the gallium compound, The indium precursor and the zinc precursor can be deposited on a substrate simultaneously, or the gallium compound, the indium precursor, and the zinc precursor can be mixed and deposited on the substrate to form a thin film with a single-layer structure, and the indium precursor, the gallium compound, and the zinc precursor can be deposited on the substrate. may be sequentially deposited on a substrate to form a thin film with a multilayer structure. Specifically, the indium precursor may be trimethylindium (TMI) or dimethylaminopropyldimethylindium (3-(Dimethylamino)propryl](dimethyl)indium; (DADI), and the zinc precursor may be diethylzinc (DEZ). ), but is not limited to this. The multilayered thin film may be an indium-gallium-zinc oxide film (IGZO thin film), and the composition ratio of indium:gallium:zinc is 1 to 10:1 to 10:1 to 10. It may be 1 to 5:1 to 5:1 to 5, and more specifically 1:1:1.

The gallium-containing thin film according to one embodiment is manufactured using the gallium compound, and is not limited, but is preferably a gallium nitride film, a gallium oxide film, or an indium-gallium-zinc oxide film, and is preferably a gallium oxide film or an indium-gallium-zinc oxide film. It may be a zinc oxide film.

The method for producing a gallium-containing thin film of the present invention uses the gallium compound of the present invention, which has high volatility and thermal stability, as a precursor, and the produced gallium-containing thin film has extremely excellent physical, electrical, and chemical properties.

In the method for manufacturing a gallium-containing thin film according to an embodiment, the injection temperature of the gallium compound of the present invention may be room temperature (25°C to 120°C, and due to the high volatility of the gallium compound of the present invention, the temperature of the substrate on which the gallium compound will be deposited is 100 to 450°C, and the pressure inside the chamber may be 0.1 to 10 torr.

The reaction gas used in the method for manufacturing a gallium-containing thin film according to an embodiment is not limited, but includes hydrogen (H ₂ ), hydrazine (N ₂ H ₄ ), dimethylhydrazine (Me ₂ N ₂ H ₂ ), and ozone ( O ₃ ), oxygen (O ₂ ), water (H ₂ O), ammonia (NH ₃ ), nitrogen (N ₂ ), silane (SiH ₄ ), borane (BH ₃ ), diborane (B ₂ H ₆ ), and One or more mixed gases selected from phosphine (PH ₃ ) can be used, and the reaction gas is not limited, but can be supplied at a flow rate of 10 to 10,000 sccm, specifically 50 to 1,000 sccm. It can be.

Specifically, when deposition is performed in the presence of oxidizing reaction gases such as water vapor (H ₂ O), oxygen (O ₂ ), or ozone (O ₃ ), a gallium oxide film may be formed, and ammonia (NH ₃ ) or hydrazine (N ₂ H ₄ ) If deposition is carried out in the presence of a nitrogen-containing reaction gas such as, a gallium nitride film may be formed.

The purge gas is an inert gas, but is not limited thereto, and may be one or a mixture of two or more gases selected from argon (Ar) and helium (He).

The substrate used in the method of manufacturing a gallium-containing thin film according to an embodiment includes a substrate containing one or more semiconductor materials selected from the group consisting of Si, SiO2, Pt, TiN, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; SOI (Silicon On Insulator) substrate; Quartz substrate; or a glass substrate for display; Polyimide, Polyethylene Terephthalate (PET), PolyEthylene Naphthalate (PEN), Poly Methyl MethAcrylate (PMMA), Polycarbonate (PC, PolyCarbonate), Polyether Sulfone Flexible plastic substrates such as (PES) and polyester; It may be, but is not limited to this.

The method for manufacturing a gallium-containing thin film according to an embodiment has high volatility and high thermal stability, and by using it as a precursor for thin film deposition, the gallium-containing thin film has excellent physical, electrical and chemical properties, and is high-density and high-purity, high-quality, uniform gallium-containing thin film. can be formed.

Hereinafter, the configuration of the present invention will be described in more detail through examples. However, the following examples are intended to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

Hereinafter, the synthesis of the gallium compound according to the present invention was performed using a standard Schlenk flask or purge box under an inert argon or nitrogen atmosphere, except where otherwise noted. The structure of the obtained gallium compound was analyzed through ¹ H NMR spectrum and elemental analysis. In addition, the thickness of the deposited gallium-containing thin film was measured using an ellipsometer (Ellipsometer, Thermowave, Optiprobe 2600) and X-ray photoelectron spectroscopy (XPS, X-ray Photoelectron Spectroscopy, ThermoFisher Scientific, K-Alpha+). The composition of the thin film was analyzed.

[Example 1] Synthesis of gallium compound 1

The oven-dried 500ml Schlenk flask and 250ml Schlenk flask were placed in a purge box and purged for more than 30 minutes to remove as much moisture inside the glassware as possible. In the purge box, 20 g (0.1742 mol) of trimethyl gallium was added to a 500 ml Schlenk flask (A), and 10.12 g (0.1742 mol) of allyl alcohol was added to a 250 ml Schlenk flask (B). Afterwards, the two flasks were moved to a fume hood to create a nitrogen atmosphere for each. 200ml of n-hexane was added to flask A and cooled to 0°C using an acetone/dry ice bath. Afterwards, 30 mL of n-hexane was added to flask B to dilute it. Next, the ligand solution from flask B was slowly added to flask A using a cannula. At this time, there was fever, and the process was carried out while maintaining the temperature inside the flask not exceeding 20°C. After adding the ligand solution from flask B, the acetone/dry ice bath was removed, the temperature was raised to room temperature, and the mixture was stirred for 16 hours. When the reaction was completed, the remaining solvent was removed through vacuum drying, and a concentrate was obtained. The obtained concentrate was purified by distillation under the conditions of tower bottom temperature: 48°C, tower top temperature: 25°C, pressure: 730 mtorr [converted temperature: 186°C], and the title gallium compound 1 was obtained as a transparent liquid (yield 86%). ).

¹ H NMR 400MHz(C ₆ D ₆ ): δ -0.1068 (s, 6H), 4.1053 (d, 2H), 4.9703 (d, 1H), 5.1502 (d, 1H), 5.7023 (m, 1H)

[Example 2] Synthesis of gallium compound 2

A concentrate was obtained by reacting in the same manner as in Example 1, except that 18.21 ml (0.1742 mol) of 2-methyl-3-buten-2-ol was used instead of 10.12 g (0.1742 mol) of allyl alcohol. did. The obtained concentrate was purified by distillation under the conditions of tower bottom temperature: 60°C, tower top temperature: 55°C, pressure: 846 mtorr [converted temperature: 223°C], and the title gallium compound 2 was obtained as a transparent liquid (yield 82%). ).

¹ H NMR 400MHz(C ₆ D ₆ ): δ -0.0336 (s, 6H), 1.2123 (s, 6H), 4.8207 (d, 1H), 4.9281 (d, 1H), 5.9176 (dd,1H)

Experimental Example 1: Material analysis of gallium compounds

To measure the thermal stability and decomposition temperature of

gallium compounds

1 and 2 prepared in Examples 1 and 2, thermogravimetric analysis (TGA) was used (TGA conditions: heating to 300°C at a rate of 10°C/min) Argon injection at a pressure of 1.5 bar/min). Graphs of the TGA analysis results are shown in Figures 1 and 2, respectively.

From Figure 1, it can be seen that the mass of gallium compound 1 prepared in Example 1 begins to decrease around 120°C, and the mass decreases by about 50% at 135.7°C. In addition, from FIG. 2, it can be seen that gallium compound 2 prepared in Example 2 begins to lose mass around 157°C and loses mass by about 50% at 172.6°C. From this, it can be seen that the gallium compound of the present invention has excellent thermal stability.

[Examples 3 to 10] Preparation of gallium-containing thin films

Gallium Compound 1 prepared in Example 1 was used as a precursor for deposition of gallium-containing thin films, ozone (O ₃ ) was used as a reaction gas, the concentration of ozone was 200 g/㎥, and argon ( A gallium-containing thin film was formed by atomic layer deposition (ALD) using Ar).

A silicon oxide film was used as a substrate. A silicon oxide film substrate was loaded into the deposition chamber, and the substrate temperature was set to 250°C. In order to appropriately maintain the vapor pressure of the gallium compound and prevent condensation, gallium compound 1 was placed in a stainless steel bubbler and maintained at 30°C. The flow rate of ozone (O ₃ ), a reaction gas, was fixed at 200 sccm, the flow rate of carrier gas (Ar) was fixed at 50 sccm, the flow rate of purge gas (Ar) was fixed at 100 sccm, and the process pressure was 1 Torr. It was maintained as . Thin film deposition using a gallium precursor was performed by repeating 100 cycles of four sequential steps: gallium precursor injection - purge (Ar) - ozone (O ₃ ) injection - purge (Ar) to deposit a gallium-containing thin film. Table 1 below shows detailed deposition conditions and results.

[Comparative Example 1] Preparation of gallium-containing thin film

A gallium-containing thin film was deposited using trimethylgallium (TMG) in the same manner as Example 8. Table 1 below shows detailed deposition conditions and results.

		실시예Example								비교예 1Comparative Example 1
		33	44	55	66	77	88	99	1010	비교예 1Comparative Example 1
공정 압력 (Torr)Process pressure (Torr)		1One	1One	1One	1One	1One	1One	1One	1One	1One
실리콘 기판 온도 (℃)Silicon substrate temperature (℃)		250250	250250	250250	250250	250250	250250	250250	250250	250250
갈륨 전구체gallium precursor	가열온도 (℃)Heating temperature (℃)	3030	3030	3030	3030	3030	3030	3030	3030	3030
갈륨 전구체gallium precursor	주입 시간 (초)Injection time (seconds)	0.50.5	1One	22	33	44	66	88	1010	66
퍼지 (Ar)Fudge (Ar)	유량 (sccm)Flow rate (sccm)	100100	100100	100100	100100	100100	100100	100100	100100	100100
퍼지 (Ar)Fudge (Ar)	시간 (초)time (seconds)	55	55	55	55	55	55	55	55	55
오존(O₃)Ozone (O ₃ )	유량 (sccm)Flow rate (sccm)	200200	200200	200200	200200	200200	200200	200200	200200	200200
오존(O₃)Ozone (O ₃ )	시간 (초)time (seconds)	66	66	66	66	66	66	66	66	66
퍼지 (Ar)Fudge (Ar)	유량 (sccm)Flow rate (sccm)	100100	100100	100100	100100	100100	100100	100100	100100	100100
퍼지 (Ar)Fudge (Ar)	시간 (초)time (seconds)	55	55	55	55	55	55	55	55	55
증착 횟수Number of depositions	주기to give	100100	100100	100100	100100	100100	100100	100100	100100	100100
박막 두께 (Å)Thin film thickness (Å)		8888	8989	9999	100100	108108	105105	107107	107107	107107
GPC (Å)GPC (Å)		0.880.88	0.890.89	0.990.99	1.001.00	1.081.08	1.051.05	1.071.07	1.071.07	1.071.07

The growth rate per cycle (GPC) according to the injection time of gallium compound 1 was measured and shown in FIG. 3. From Table 1 and Figure 3, the GPC of the gallium precursor according to the present invention increases from 0.5 to 3 seconds of injection time, and the GPC is maintained at a constant level from 4 seconds of injection time, resulting in saturation from 4 seconds of injection time of the gallium precursor. It was confirmed that the growth rate of the gallium-containing thin film was constant.

The XPS analysis results of the gallium-containing thin film prepared in Example 8 are listed in Table 2 below and shown in FIG. 4. Table 2 shows the content of each atom in the thin film based on the composition of the prepared gallium-containing thin film analyzed using X-ray photoelectron spectroscopy.

	실시예 8 (갈륨 화합물 1)Example 8 (Gallium Compound 1)	비교예 1 (TMG)Comparative Example 1 (TMG)
	Atomic %Atomic %	Atomic %Atomic %
C1sC1s	6.56.5	5.45.4
Ga3dGa3d	37.837.8	39.939.9
O1sO1s	55.755.7	54.754.7
Ga:O 비율Ga:O ratio	1:1.471:1.47	1:1.371:1.37

From Table 2, the atomic content of the gallium-containing thin film prepared in Example 8 of the present invention was confirmed that the stoichiometric ratio of gallium element and oxygen element was 1 to 1.47, and a Ga ₂ O ₃ thin film was formed. This was very close to the theoretical value of the stoichiometric ratio of gallium and oxygen elements of 1 to 1.5 compared to the gallium-containing thin film (Ga:O = 1:1.37) manufactured using TMG in Comparative Example 1. In addition, the XPS analysis results for the gallium-containing thin film prepared in Example 8 are published in the published literature [ J. Mater. Chem. Binding Energy (eV) similar to Ga ₂ O ₃ described in [C, 2019, 7, 69-77] was confirmed (Figure 4).

[Example 11] Preparation of indium gallium zinc oxide (IGZO) thin film

Gallium Compound 1 prepared in Example 1 was used as a gallium precursor, dimethylaminopropyldimethylindium (DADI) was used as an indium precursor, and diethyl zinc (DEZ) was used as a zinc precursor. Ozone (O ₃ ) was used as a reaction gas, and the concentration of ozone was 210 g/㎥, and an IGZO thin film was formed by atomic layer deposition (ALD) using argon (Ar) as a carrier gas and purge gas. formed.

A silicon substrate was used. A silicon substrate was loaded inside the deposition chamber, and the substrate temperature was set to 250°C. In order to properly maintain the vapor pressure of the precursor and prevent condensation, it was filled in a stainless steel bubbler and maintained at 30°C. The flow rate of ozone (O ₃ ), a reaction gas, was fixed at 200 sccm, the flow rate of carrier gas (Ar) was fixed at 50 sccm, the flow rate of purge gas (Ar) was fixed at 100 sccm, and the process pressure was 0.3 Torr. It was maintained as .

Thin film deposition repeats the four sequential steps of indium precursor injection - purge (Ar) - ozone (O ₃ ) injection - purge (Ar) four times, then gallium precursor injection - purge (Ar) - ozone (O ₃ ) injection. - Purge (Ar) - Zinc precursor injection - Purge (Ar) - Ozone (O ₃ ) injection - Purge (Ar) 8 sequential steps were considered as 1 cycle, and 100 cycles were repeated to deposit the IGZO thin film. Table 3 below shows detailed deposition conditions and results.

[Comparative Example 2] Preparation of indium gallium zinc oxide (IGZO) thin film

An IGZO thin film was deposited in the same manner as Example 11, using trimethylgallium (TMG) as a gallium precursor. Table 3 below shows detailed deposition conditions and results.

		실시예 11Example 11	비교예 2Comparative Example 2
공정 압력 (Torr)Process pressure (Torr)		0.30.3	0.30.3
실리콘 기판 온도 (℃)Silicon substrate temperature (℃)		250250	250250
인듐 전구체indium precursor	가열온도 (℃)Heating temperature (℃)	5050	5050
인듐 전구체indium precursor	주입 시간 (초)Injection time (seconds)	1One	1One
퍼지 (Ar)Fudge (Ar)	유량 (sccm)Flow rate (sccm)	100100	100100
퍼지 (Ar)Fudge (Ar)	시간 (초)time (seconds)	1515	1515
오존(O₃)Ozone (O ₃ )	유량 (sccm)Flow rate (sccm)	200200	200200
오존(O₃)Ozone (O ₃ )	시간 (초)time (seconds)	1010	1010
퍼지 (Ar)Fudge (Ar)	유량 (sccm)Flow rate (sccm)	100100	100100
퍼지 (Ar)Fudge (Ar)	시간 (초)time (seconds)	1515	1515
갈륨 전구체gallium precursor	가열온도 (℃)Heating temperature (℃)	3030	55
갈륨 전구체gallium precursor	주입 시간 (초)Injection time (seconds)	1One	1One
퍼지 (Ar)Fudge (Ar)	유량 (sccm)Flow rate (sccm)	100100	100100
퍼지 (Ar)Fudge (Ar)	시간 (초)time (seconds)	2020	2525
오존(O₃)Ozone (O ₃ )	유량 (sccm)Flow rate (sccm)	200200	200200
오존(O₃)Ozone (O ₃ )	시간 (초)time (seconds)	120120	1515
퍼지 (Ar)Fudge (Ar)	유량 (sccm)Flow rate (sccm)	100100	100100
퍼지 (Ar)Fudge (Ar)	시간 (초)time (seconds)	1515	2020
아연 전구체zinc precursor	가열온도 (℃)Heating temperature (℃)	3030	3030
아연 전구체zinc precursor	주입 시간 (초)Injection time (seconds)	1One	1One
퍼지 (Ar)Fudge (Ar)	유량 (sccm)Flow rate (sccm)	100100	100100
퍼지 (Ar)Fudge (Ar)	시간 (초)time (seconds)	2020	2020
오존(O₃)Ozone (O ₃ )	유량 (sccm)Flow rate (sccm)	200200	200200
오존(O₃)Ozone (O ₃ )	시간 (초)time (seconds)	1010	1010
퍼지 (Ar)Fudge (Ar)	유량 (sccm)Flow rate (sccm)	100100	100100
퍼지 (Ar)Fudge (Ar)	시간 (초)time (seconds)	2020	2020
증착 횟수Number of depositions	주기to give	100100	100100
박막 두께 (Å)Thin film thickness (Å)		39.139.1	27.927.9
GPC (Å)GPC (Å)		0.3910.391	0.2790.279

A graph comparing the theoretical and actual experimental values of GPC measured in Example 11 and Comparative Example 2 is shown in Figure 5. In the case of the IGZO thin film made with trimethyl gallium (TMG) as a gallium precursor, the theoretical value of GPC was 0.455 Å/cycle, but the actual experimental value was measured to be 0.279 Å/cycle. On the other hand, the IGZO thin film prepared using gallium compound 1 of the present invention as a gallium precursor was measured as a GPC theoretical value of 0.475 Å/cycle and an actual experimental value of 0.391 Å/cycle. Therefore, it was confirmed that the IGZO thin film made with trimethyl gallium as the gallium precursor had a large difference between the theoretical value and the experimental value, but the error in the IGZO thin film made with gallium compound 1 of the present invention as the gallium precursor was significantly reduced.

In addition, a graph comparing the theoretical value and the actual experimental value of the gallium content in the IGZO thin film prepared in Example 11 and Comparative Example 2 divided by the total content of indium, gallium, and zinc through XRF is shown in FIG. 6.

For the IGZO thin film made with trimethyl gallium as a gallium precursor, the theoretical value was 0.07 and the actual experimental value was 0.3, and for the IGZO thin film made with gallium compound 1 of the present invention as a gallium precursor, the theoretical value was 0.12 and the experimental value was 0.19. Therefore, it was confirmed that the error value of the gallium content of the IGZO thin film containing the gallium compound of the present invention was significantly improved compared to the IGZO thin film containing trimethyl gallium as a precursor.

In other words, when the gallium compound according to the present invention is used as a precursor, it is easy to control the gallium content ratio in the thin film, making it possible to produce a high-quality gallium-containing thin film.

That is, it can be seen that when the gallium compound according to the present invention is used as a precursor, a high-quality gallium-containing thin film with higher purity is produced. On the other hand, when trimethyl gallium, a known material, was used, thin film deposition results were similar to the examples of the present invention, but as a result of XPS analysis, it was confirmed that the purity of the thin film was lower than that of the examples of the present invention.

Therefore, the gallium compound according to the present invention has excellent thermal stability and volatility, making it useful as a precursor for gallium-containing thin films, and has a high vapor pressure, enabling uniform thin film deposition through uniform composition control through uniform precursor supply during thin film production. And, high-density and high-purity gallium-containing thin films can be easily manufactured.

The description of the present invention described above is for illustrative purposes, and those skilled in the art will understand that the present invention can be easily modified into other specific forms without changing the technical idea or essential features of the present invention. will be. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive.

Claims

A gallium compound represented by the following formula (1):

[Formula 1]

In Formula 1,

R 1 is C1-C10 alkyl;

R 2 is C1-C10 alkyl, -OR' or -SR';

R' is C1-C10 alkyl or C2-C10 alkenyl;

X 1 is O or S;

R a and R b are independently hydrogen or C1-C10 alkyl;

The alkenyl of R' may be further substituted with one or more C1-C10 alkyl.
According to clause 1,

R 1 is C1-C6alkyl;

R 2 is C1-C6alkyl or -OR';

R' is C1-C6alkyl or allyl;

X 1 is O;

R a and R b are independently hydrogen or C1-C6alkyl;

A gallium compound in which allyl of R' may be further substituted with one or more C1-C6alkyl.
According to clause 1,

The gallium compound is represented by the following formula (2):

[Formula 2]

In Formula 2,

R 1 is C1-C4alkyl;

R 2 is C1-C4alkyl or
ego;

R a , R b , R c and R d are independently hydrogen or C1-C4alkyl.
According to clause 1,

The gallium compound is selected from the following compounds:
A method for producing a gallium compound comprising: reacting a trialkyl gallium compound of Formula 3 below and an allyl compound of Formula 4 below to prepare a gallium compound of Formula 1-1 below.

[Formula 1-1]

[Formula 3]

[Formula 4]

In Formulas 1-1, 3 and 4,

R 1 , R 2a and R 3a are each independently C1-C10 alkyl;

R 2b is C1-C10 alkyl or
ego;

X 1 is O or S;

R a and R b are independently hydrogen or C1-C10 alkyl.
A composition for depositing a gallium-containing thin film comprising the gallium compound according to any one of claims 1 to 4.
A method of forming a gallium-containing thin film using the composition for gallium-containing thin film deposition of claim 6.
A method for producing a gallium-containing thin film, comprising forming a thin film by depositing the gallium compound according to any one of claims 1 to 4 on a substrate.
According to clause 8,

The method of manufacturing a gallium-containing thin film includes forming a thin film by depositing the gallium compound and at least one selected from an indium precursor and a zinc precursor on a substrate.
According to clause 8,

A method of producing a gallium-containing thin film, wherein the deposition is performed by chemical vapor deposition (CVD) or atomic layer deposition (ALD).
According to clause 8,

The gallium-containing thin film is a gallium oxide thin film, a gallium thin film, a gallium nitride thin film, or an indium gallium zinc oxide (IGZO) thin film.