TW202336028A - Method of forming dielectric films, new precursors and their use in the semi-conductor manufacturing - Google Patents

Abstract

The purpose of the present invention is to provide a precursor compound which is suitable for the control of the thickness and the chemical composition in the formation of a film by vapor deposition at a high temperature, has high-temperature stability, has a liquid form or a low melting point (50 DEG C or lower under ambient pressure) and contains niobium, vanadium or tantalum. Provided is a compound for use in the formation of a metal-containing film by deposition, the compound being represented by formula (1). (In formula (1), M represents V or Nb, R1, R2 and R3 each independently represent H or a C1-C10 alkyl group, L represents a ligand derived from a C3 or higher alkene structure, a C4 or higher alkadiene structure, a C5 or higher cycloalkadiene structure or a condensed aromatic ring structure each of which is substituted or unsubstituted, and e represents a value of 0 or 1; or M represents Ta, R1, R2 and R3 each independently represent H or a C1-C10 alkyl group, L represents a ligand derived from a C3 or higher alkene structure, a C4 or higher alkadiene structure, a C6 or higher cycloalkadiene structure or a condensed aromatic ring structure each of which is substituted or unsubstituted, and e represents a value of 0 or 1.).

Description

Compound, method for forming metal-containing film, and method for producing compound

The present invention relates to a compound, a method for forming a metal-containing film, and a method for producing the compound.

Metal oxides such as niobium oxide (Nb ₂ O ₅ ) or vanadium oxide (V ₂ O ₅ ) are widely used in various technical fields. Typically, these oxides are used as high-k materials for insulating films.

On the other hand, metal nitride films such as niobium nitride or vanadium nitride (NbN _x , VN _x (both x values are approximately 1)) have been used in recent years as diffusion barriers or adhesive layers for microelectronic devices. .

Mixed oxides containing Nb have attracted great attention in energy storage applications, such as forming a thin interface layer with high ion conductivity between the cathode active material and the electrolyte in all-solid-state batteries and Li-ion batteries. For example, lithium niobate is of particular interest as an interface layer because it exhibits significantly higher ionic conductivity.

As a possible technology for evaporating the interface layer as described above on the material, a vapor deposition method such as atomic layer deposition has been studied. Various compounds have been proposed as niobium sources, vanadium sources, and tantalum sources for vapor deposition of metal nitrides (Chem. Mater. 1993, 5, 614-619; German Patent Application Publication No. 102006037955). [Prior technical literature] [Patent Document]

[Patent Document 1] German Patent Application Publication No. 102006037955 Specification [Non-patent literature]

[Non-patent document 1] Chem. Mater. 1993, 5, 614-619

[Problem to be solved by the invention]

The object of the present invention is to provide a precursor compound that is suitable for controlling thickness and composition when forming a film by vapor deposition at high temperatures, has high temperature stability, and is liquid or has a low melting point (below 50°C under normal pressure). Contains niobium, vanadium or tantalum. [Technical means to solve the problem]

According to the present invention, specific precursor compounds are found to be suitable for depositing Nb, V or Ta-containing films by vapor deposition processes including atomic layer deposition (ALD).

In one embodiment, the present invention relates to a compound represented by the following formula (1) for forming a metal-containing film by vapor deposition. (In the formula, M is V or Nb, R ¹ , R ² and R ³ are each independently H or C1 to C10 alkyl, L is from a substituted or unsubstituted olefin structure of C3 or above, C4 or above. For the ligand of an olefin structure, a cyclic diene structure with C5 or above, or a condensed aromatic ring structure, the value of e is 0 or 1; or, M is Ta, and R ¹ , R ² and R ³ are independently H or C1~ C10 alkyl group, L is a ligand derived from a substituted or unsubstituted C3 or above olefin structure, C4 or above diene structure, C6 or above cyclodiene structure or condensed aromatic ring structure, the value of e is 0 or 1).

In one embodiment, the present invention relates to a method for forming a metal-containing film, which includes the following steps: Introduction step: introduce the above compound into a reactor with a substrate inside; and Deposition step: depositing at least part of the above compound on the above substrate.

In one embodiment, the present invention relates to a method for producing a compound, which method includes making a precursor compound represented by the following formula (i) and an alcohol represented by the following formula (α-1) and a step of at least one reaction among the alcohols represented by the following formula (α-2). (In the formula (i), M, R ¹ , L and e are synonymous with the above formula (1), and R ^a and R ^b are each independently a C1 to C5 alkyl group). (In formulas (α-1) and (α-2), R ² and R ³ are synonymous with the above formula (1)).

The definitions of terms are explained below.

Standard abbreviations for elements from the periodic table of elements are used in this specification. Therefore, elements can be represented by these abbreviations (for example, Nb refers to niobium, V refers to vanadium, Ta refers to tantalum, N refers to nitrogen, C refers to carbon, and H refers to hydrogen. The same is true for other elements).

When used in this specification, the abbreviation of "Me" refers to methyl; the abbreviation of "Et" refers to ethyl; the abbreviation of "Pr" refers to propyl; the abbreviation of "nPr" refers to "normal" or straight Chain propyl; the abbreviation of "iPr" refers to isopropyl; the abbreviation of "Bu" refers to butyl; the abbreviation of "nBu" refers to "normal" or straight-chain butyl; the abbreviation of "tBu" refers to tertiary Butyl, also known as 1,1-dimethylethyl; the abbreviation of "sBu" refers to secondary butyl, also known as 1-methylpropyl; the abbreviation of "iBu" refers to isobutyl, also It is called 2-methylpropyl; the term "amyl" refers to amyl (amyl) or pentyl (pentyl); the term "t-amyl" refers to tertiary pentyl, also known as 1,1-di Methylpropyl; the abbreviation of "Cp" refers to cyclopentadienyl; the abbreviation of "amd" refers to amide group.

In this specification, the combination of C and numbers such as "C1" means the number of carbon atoms constituting the group or structure. For example, C1 alkyl represents an alkyl group with a carbon number of 1 (i.e., methyl), C2 alkyl represents an alkyl group with a carbon number of 2 (i.e., an ethyl group), and C3 olefin structure represents an olefin structure with a carbon number of 3 ( i.e., propylene structure). [Effects of the invention]

The compound of the present invention has suitability for the gas phase method, high temperature stability and low melting point (or liquid state), and is therefore suitable for forming metal films containing niobium, vanadium or tantalum through gas phase deposition. Furthermore, since the method for forming a metal-containing film of the present invention uses a specific compound as a precursor for the vapor deposition method, the metal-containing film can be formed efficiently.

Embodiments of the present invention will be described below. The present invention is not limited to these embodiments. It is also better to be a combination of better forms.

<Compound> The compound of this embodiment is represented by the following formula (1) and is used to form a metal-containing film by vapor deposition. The compound is liquid at room temperature or has a melting point below 50°C. In addition, because this compound has thermal stability, it can be directly introduced into the reactor in the form of gas phase or liquid during vapor deposition, and can provide a wide ALD window that shows a fixed growth rate with respect to temperature rise.

In one embodiment (hereinafter, also referred to as "the first embodiment"), in the above formula (1), M is V or Nb, and R ¹ , R ² and R ³ are each independently H or C1 to C10 alkane. group, L is a ligand derived from a substituted or unsubstituted C3 or above olefin structure, C4 or above diene structure, C5 or above cyclic diene structure or condensed aromatic ring structure, and the value of e is 0 or 1.

In another embodiment (hereinafter, also referred to as the "second embodiment"), in the above formula (1), M is Ta, and R ¹ , R ² and R ³ are each independently H or a C1-C10 alkyl group. , L is a ligand derived from a substituted or unsubstituted C3 or above olefin structure, C4 or above diene structure, C6 or above cyclic diene structure or condensed aromatic ring structure, and the value of e is 0 or 1.

(First embodiment) In the first embodiment, the central metal M of the compound represented by the above formula (1) is V (vanadium) or Nb (niobium). M is preferably Nb.

As the C1 to C10 alkyl group represented by R ¹ , R ² and R ³ , each independently includes: methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl A linear or branched alkyl group with a carbon number of 1 to 10. R ¹ is preferably a branched alkyl group having 3 to 5 carbon atoms, and more preferably a tertiary butyl group. R ² and R ³ are each independently preferably a linear or branched chain alkyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a tertiary butyl group or a secondary butyl group.

Examples of the above-mentioned C3 or higher olefin structure that provides the ligand represented by L include: propylene structure, butene structure, pentene structure, and hexene which are linear or branched and have no limit on the position of the unsaturated bond. The structure is an olefin structure with a carbon number of 3 to 10. As the C3 or higher olefin structure, a linear C3 to C6 olefin structure is preferred, and propylene is more preferred.

Examples of the above-mentioned C4 or higher diene structure include: butadiene structure, pentadiene structure, hexadiene structure, heptadiene structure, etc. which are linear or branched and have no limit on the position of the unsaturated bond. Diolefin structure with a number of 4 to 10. As the C4 or higher diene structure, a linear diene structure having 4 to 6 carbon atoms is preferred, and a linear butadiene structure or a pentadiene structure is more preferred.

Examples of the above-mentioned cyclodiene structure having C5 or more include: cyclopentadiene structure, cyclohexadiene structure, cycloheptadiene structure, cyclooctadiene structure, etc., with no limit on the position of the unsaturated bond, and the number of carbon atoms is 5 to 10. Cyclodiolefin structure. Among them, a cyclodiene structure having 5 to 7 carbon atoms is preferred, and a cyclopentadiene structure is further preferred.

The above-mentioned condensed aromatic ring structure is not particularly limited as long as it includes a structure in which an aromatic ring is condensed with another ring. Condensation refers to a polycyclic structure formed by two adjacent rings sharing an edge (bond between two adjacent carbon atoms). The other ring may be an aromatic ring that is the same as or different from the above-mentioned aromatic ring, or may be an alicyclic structure.

Examples of the aromatic ring include aromatic hydrocarbon rings or aromatic heterocycles with 5 to 30 ring members. Examples include benzene ring, naphthalene ring, anthracene ring, pyrene ring, phenanthrene ring, pyrene ring, fluorine ring, and perylene ring. Aromatic hydrocarbon rings such as ring and carbocyclic ring; furan ring, pyrrole ring, thiophene ring, phosphole ring, pyrazole ring, azole ring, iso Azole ring, thiazole ring, pyridine ring, pyridine ring ring, pyrimidine ring, da ring, three Rings and other aromatic heterocycles; or combinations thereof, etc.

Examples of the alicyclic structure include aliphatic cyclic hydrocarbon structures with 5 to 20 ring members. Examples include: cycloalkanes such as cyclopentane and cyclohexane; and cyclic olefins such as cyclopropene, cyclopentene, and cyclohexene. ;drop Bridged ring saturated hydrocarbons such as alkane, adamantane, and tricyclodecane; bridged ring unsaturated hydrocarbons such as norbornene and tricyclodecene.

As the condensed aromatic ring structure, an aromatic hydrocarbon ring structure having 6 to 12 ring members is preferred, and an indene structure is more preferred.

Examples of the substituent that replaces part or all of the hydrogen atoms of L include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, alkyl group, alkylsilyl group, alkylgermanyl group, and alkyl group. amide group, alkylsilyl amide group, hydroxyl group, carboxyl group, cyano group, nitro group, alkoxy group, alkoxycarbonyl group, alkoxycarbonyloxy group, acyl group, acyloxy group, etc.

The value of e is preferably 1.

(Second embodiment) In the second embodiment, the central metal M of the compound represented by the above formula (1) is Ta (tantalum). In the first embodiment, the carbon number of the cyclodiene structure that provides the ligand represented by L is 5 or more (C5 or more). In contrast, in the second embodiment, the carbon number of the cyclodiene structure is 6 and above (C6 and above). Regarding other structures, substituents, etc., the corresponding structures, substituents, etc. in the first embodiment can be appropriately adopted.

(Other implementation forms) Below, preferred embodiments of the compounds are exemplified.

The above compound is preferably represented by the following general formula (1-1). (In formula (1-1), M is V or Nb, R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently H, C1 to C10 alkyl group, halogen atom, alkylsilyl group, alkyl group, etc. Germanium group, alkylaminocarbonyl group or alkylsilylamide group, R ¹ , R ² and R ³ are synonymous with the above formula (1)).

As the C1 to C10 alkyl group represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ , the C1 to C10 alkyl group represented by R ¹ , R ² and R ³ of the above formula (1) can be suitably used. .

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a fluorine atom is preferred.

Examples of the alkylsilyl group include trimethylsilyl group, triethylsilyl group, and the like.

Examples of the alkylgermanium group include trimethylgermanium group, triethylgermanium group, and the like.

Examples of the alkylaminocarbonyl group include dimethylaminocarbonyl group, diethylaminocarbonyl group, and the like.

Examples of the alkylsilylamide group include a trimethylsilylamide group, a triethylsilylamide group, and the like.

R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably H (hydrogen atom).

The above compound is preferably represented by the following general formula (1-2). (In the formula, M is V, Nb or Ta, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently H, C1～C10 alkyl or halogen atom, R ¹ , R ² and R ³ are synonymous with the above formula (1)).

As the C1 to C10 alkyl group represented by R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ , those represented by R ¹ , R ² and R ³ of the above formula (1) can be suitably used. C1～C10 alkyl.

As the above-mentioned halogen atom, the same halogen atom as in the above-mentioned formula (1-1) can be used.

R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are preferably H (hydrogen atom).

The above compound is preferably represented by the following general formula (1-3). (In the formula, M is V, Nb or Ta, R ¹⁶ and R ¹⁷ are independently H, C1-C10 alkyl or halogen atom, R ¹ and R ² are synonymous with the above formula (1)).

As the C1-C10 alkyl group represented by ^R16 and ^R17 , the C1-C10 alkyl group represented by ^R1 , ^R2 and ^R3 of the above formula (1) can be suitably used.

As the above-mentioned halogen atom, the same halogen atom as in the above-mentioned formula (1-1) can be used.

R ¹⁶ and R ¹⁷ are preferably H (hydrogen atom).

The above compound is preferably represented by the following general formula (1-4). (In the formula, M is V, Nb or Ta, R ¹⁸ , R ¹⁹ and R ²⁰ are independently H, C1-C10 alkyl or halogen atom, R ¹ , R ² and R ³ are synonymous with the above formula (1) ).

As the C1-C10 alkyl group represented by ^R18 , ^R19 and ^R20 , the C1-C10 alkyl group represented by ^R1 , ^R2 and ^R3 of the above formula (1) can be suitably used.

As the above-mentioned halogen atom, the same halogen atom as in the above-mentioned formula (1-1) can be used.

R ¹⁸ , R ¹⁹ and R ²⁰ are preferably H (hydrogen atom).

The above compound is preferably in a liquid state at 25°C, or the temperature at which the vapor pressure shows 133.3 Pa is 130°C or lower. It is more preferable that the temperature at which the vapor pressure shows 133.3 Pa is below 120°C. Thereby, the compound can exist in a liquid state at room temperature or in a solid form with a low melting point, and the vapor deposition process for forming a metal-containing film can be efficiently performed.

In the thermogravimetric analysis of the above compounds, it is preferable to exist in a region where the weight loss is less than 20% at a temperature of 150°C or higher, and more preferably, it exists in a region where the weight loss is less than 20% at a temperature of 180°C or higher, and still more preferably Exists in the area where the weight loss is less than 20% at temperatures above 200°C. Thereby, the compound can exhibit excellent thermal stability.

Due to the above characteristics, the above compounds are suitable for thin film vapor deposition. As examples of better vapor deposition methods, there are no limitations. Examples include: atomic layer deposition (ALD), plasma enhanced atomic layer deposition (PE-ALD), chemical vapor deposition (CVD), pulse chemical vapor deposition ( P-CVD), thermal, plasma or remote plasma processes in low pressure chemical vapor deposition (LPCVD), or a combination of these.

"Method for producing a compound" The method for producing the above-mentioned compound includes the steps of making a precursor compound represented by the following formula (i), an alcohol represented by the following formula (α-1) and the following formula (α-2 ) at least one reaction among the alcohols represented by . According to this production method, the desired compound can be efficiently produced by simply performing a ligand exchange reaction based on a precursor compound and a predetermined alcohol. (In the formula (i), M, R ¹ , L and e are synonymous with the above formula (1), and R ^a and R ^b are each independently a C1 to C5 alkyl group). (In formulas (α-1) and (α-2), R ² and R ³ are synonymous with the above formula (1)).

Examples of the C1-C5 alkyl group represented by R ^a and R ^b include methyl group, ethyl group, and the like. Among them, methyl is preferred.

The precursor compound can be synthesized, for example, by the method described in US Patent No. 8460989.

The precursor compound is dissolved in an appropriate solvent such as toluene to prepare a raw material solution. The target compound can be produced by mixing and stirring the raw material solution and alcohol to perform a ligand exchange reaction. Preferably, 1 to 3 moles of alcohol are mixed with respect to 1 mole of the precursor compound. The reaction temperature can be room temperature or heated to about 50°C. The reaction time is preferably 1 to 24 hours, and more preferably 2 to 16 hours.

After the reaction, if necessary, the solvent may be removed by distillation using an evaporator, drying by heating and under reduced pressure, distillation, sublimation, column chromatography, etc. for purification.

"Metal-Containing Film Formation Method" The formation method of the metal-containing film in this embodiment includes the following steps: Introduction step: introduce the above compound into a reactor with a substrate inside; and Deposition step: depositing at least part of the above compound on the above substrate.

(Import step) In this step, the above compound is introduced into a reactor with a substrate inside. The type of substrate on which the metal-containing film is deposited can be appropriately selected depending on the end use.

In some embodiments, the substrate is selected from a cathode active material or cathode in a lithium-ion battery device or an all-solid-state battery device. The cathode active material is the main element in the composition of the cathode battery cell. The cathode material is, for example, cobalt, nickel, or manganese. The crystal structure of the layer structure forms a multi-metal oxide material with lithium inserted therein. The preferred cathode active material is "NMC" (lithium nickel manganese cobalt oxide), NCA (lithium nickel cobalt aluminum oxide), LNO (lithium nickel oxide), LMNO (lithium manganese nickel oxide) or LFP (lithium iron phosphate ). For example, the cathode active material may be NMC622 or NMC811. The thin interface layer can be deposited on the electrode active material powder, the electrode active material porous material, the electrode active material of different shapes, or a preformed electrode. The electrode active material of the preformed electrode can be combined with conductive carbon and/or Adhesive bonding may also be supported by current collecting foils.

In some embodiments, the substrate can be selected from oxides used as insulating materials in MIM, DRAM or FeRam technology (such as HfO ₂ matrix material, TiO ₂ matrix material, ZrO ₂ matrix material, rare earth oxide matrix material, three-dimensional oxide matrix material, etc. oxide base material, etc.) or a nitride base film (such as TaN) used as an oxygen barrier layer between copper and a low-k film. In the manufacture of semiconductors, photovoltaics, LCD-TFTs or flat panel devices, other substrates can be used. Examples of such substrates are not limited, but include: solid substrates such as metal nitride-containing substrates (such as TaN, TiN, WN, TaCN, TiCN, TaSiN, and TiSiN); insulators (such as SiO ₂ , Si ₃ N ₄ , SiON, HfO ₂ , Ta ₂ O ₅ , ZrO ₂ , TiO ₂ , Al ₂ O ₃ and barium strontium titanate); or other substrates containing some combination of these materials. The actual substrate utilized may also depend on the specific compound implementation utilized.

The reactor may be any closed container or chamber of a device within which a vapor deposition method can be performed. Specific examples are not limited and include: parallel plate reactors, cold wall reactors, hot wall reactors, sheet reactors, multi-wafer reactors or other types of deposition systems.

Then, the gas containing the vaporized compound is introduced into the reactor. Pure (single) compounds or blended (several) compounds can also be supplied to the vaporizer in a liquid state, where they are vaporized before being introduced into the reactor. Alternatively, the compound can be vaporized by passing a carrier gas through a container containing the compound, or by bubbling a carrier gas through the compound. Then, the gas containing the carrier gas and the vaporized compound is introduced into the reactor. If necessary, the container can also be heated to a temperature that allows the compound to have a sufficient vapor pressure. The carrier gas is not limited, and examples include: Ar, He, N ₂ and mixtures thereof. Alternatively, direct liquid injection (DLI) may be used to vaporize the compound instead of bubbling the carrier gas as described above (i.e., the bubbling method).

In the introduction step, the co-reactant may be further introduced into the reactor. As a co-reactant, it is preferably selected from the group consisting of O ₂ , O ₃ , H ₂ O, H ₂ O ₂ , NO, N ₂ O, NO ₂ , trimethyl phosphate, oxygen radicals thereof, and mixtures thereof form a group. As other co-reactants, alcohol, ammonia, polyamine, hydrazine, dimethylethyl phosphoramidate, sulfate, etc. can also be used.

For example, the container can be maintained at a temperature in the range of about 0°C to about 150°C. Those skilled in the art know that the temperature of the container can be adjusted by well-known methods to control the amount of vaporized compounds.

The compounds may be supplied in pure form (eg, liquids or low melting point solids) or in blends with appropriate solvents. Exemplary solvents are not limited and include: aliphatic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, ethers, glycol dimethyl ether, glycols, amines, polyamines, cyclic amines, and alkyl groups. amines, alkylated polyamines and mixtures thereof. Preferred solvents include: ethylbenzene, diglyme, triglyme, tetraglyme, pyridine, xylene, mesitylene, decane, and dodecane. and mixtures thereof. The concentration of the compound typically ranges from about 0.02 to about 2.0 M, and preferably ranges from about 0.05 to about 0.2 M.

In addition to arbitrary mixing of compounds and solvents before introduction into the reactor, gases containing vaporized compounds can also be mixed with reactant species in the reactor. Exemplary reaction species are not limited and may include metal precursors such as strontium-containing precursors, barium-containing precursors, aluminum-containing precursors such as TMA, and any combination thereof.

The reactor can be maintained at a pressure in the range of about 0.5 mTorr to about 20 Torr. In addition, the temperature in the reactor can be in the range of about 50°C to about 600°C, preferably in the range of about 80°C to about 550°C. Those skilled in the art can empirically optimize the temperature to achieve the desired results.

The substrate can be heated to a temperature sufficient to obtain the desired lithium-containing film at a sufficient growth rate and desired physical state and composition. A non-limiting example of a temperature range in which the substrate can be heated is 50°C to 500°C. Preferably, the temperature of the substrate is kept below 300°C.

(deposition step) In this step, at least part of the above compound is deposited on the above substrate. In an exemplary atomic layer deposition-type process, the vapor phase of a compound is introduced into a reactor where it is brought into contact with a suitable substrate. Thereafter, excess compounds can be removed from the reactor by flushing and/or venting the reactor. The coreactants are introduced into the reactor where they react in a self-stopping manner with the absorbed compounds. Excess coreactants are removed from the reactor by flushing and/or venting the reactor. When the desired film is a metal oxide film, this two-stage process sometimes provides the desired film thickness, and sometimes it is repeated until a film with the desired thickness is obtained.

Alternatively, when the desired film is a metal oxide film, after the above two-stage process, the vapor of the metal precursor can continue to be introduced into the reactor. The metal precursor is selected based on the properties of the deposited metal oxide. After being introduced into the reactor, the compound comes into contact with the substrate. Excess compounds are removed from the reactor by flushing and/or venting the reactor. The co-reactant can also be introduced into the reactor again to react with the metal precursor. Excess coreactants are removed from the reactor by flushing and/or venting the reactor. If the desired film thickness is obtained, the process can be terminated. However, if a thicker film is desired, the entire 4-stage process can be repeated. By alternately supplying compounds, metal precursors, and coreactants, films of desired composition and thickness can be deposited.

The metal-containing film obtained according to the manufacturing method of this embodiment may be a ternary or quaternary oxide film of niobium such as LiNbO, LiNbO, LiNb(M)O, and NbMO. M is selected from the group consisting of Zr, Ti, Co, W, Ta, V, Sr, Ba, La, Y, Sc, Mn, Ni, and Mo. Those skilled in the art can obtain the desired membrane composition by appropriately selecting appropriate compounds and reaction species.

The composition of the deposited film depends on the application. For example, metal-containing films may be used in fuel cell or battery applications. [Example]

Although the following examples are described to illustrate the applications disclosed in this specification, it should be fully understood that not all advantages of the processes described in this specification may be included in specific embodiments or groups of embodiments of the present invention. Although specific embodiments and examples are disclosed below, those skilled in the art will understand that the present invention extends beyond the specifically disclosed embodiments and/or uses of the invention including obvious modifications. Therefore, it should be understood that the scope of the disclosed invention should not be limited by the specific embodiments described below.

<Example 1> Synthesis of Nb(=NtBu)(Cp)(OEt) ₂ and bis(ethoxy)(tertiary butylcarboxylimide)cyclopentadienylniobium

To a solution of Nb(＝NtBu)Cp(NMe ₂ ) ₂ (2 g, 6.3 mmol) (purchased from Air Liquide Advanced Materials Inc.) in 30 mL of toluene at -78°C, ethanol (0.58 g, 12.6 mmol) was added ( Manufactured by Sigma-Aldrich Company). After the mixture was stirred at room temperature (about 25°C) for 12 hours, the solvent was removed under vacuum to obtain a yellow oil. This material was then purified by distillation at 25 mTorr up to 100°C to obtain 1.34 g (yield 66.6%) of a yellow oil. The product was characterized by NMR ¹ H (π, ppm, C ₆ D ₆ ): 6.18 (s, 5H), 4.54 (q, 4H), 1.28 (t, 6H), 1.16 (s, 9H).

The purified product was subjected to open cup TGA analysis (manufactured by Mettler Toledo Co., measured using model TGA/DSC 1 STARe System) at a temperature rise rate of 10°C/min in the atmosphere with a nitrogen flow of 200 mL/min. The results were obtained 2.1% residual caking remains. The results are shown in Figure 1 . Figure 1 is a thermogravimetric analysis (TGA) graph showing the weight percentage as the temperature increases. Through differential scanning calorimetry of the product (DSC, manufactured by Mettler Toledo Company, model: DSC 1 STARe System (measured using ME-51140728)), the melting onset temperature (-3.8°C) and decomposition onset temperature (317.3°C) were obtained ). The results are shown in Figure 4 .

Figure 8 shows the compound produced in Example 1, that is, bis(ethoxy)(tertiary butylcarboxylimide)cyclopentadienylniobium, Nb(=NtBu)(Cp)(OEt) ₂ Ozone based ALD window. Furthermore, Figure 9 is a film coating image of a patterned wafer of an Nb ₂ O ₅ film formed by depositing Nb (=NtBu) (Cp) (OEt) ₂ at 250°C and 300°C (SEM measurement, Japan Electronics Co., Ltd. Manufactured by the company, model: FE-SEM (JEOL-6701F)). The formation conditions of the Nb ₂ O ₅ film are that the wafer temperature is 250 and 300°C, the process pressure is 1 torr, the Ar flow rate is 100 sccm, the source material introduction time/source material flushing time/ozone introduction time/ozone flushing time is 2/ 60/1/60 (seconds).

<Example 2> Synthesis of Nb(=NtBu)(Cp)(OtBu) ₂ and bis(tertiary butyloxy)(tertiary butylcarboxylimide)cyclopentadienyl niobium

To a solution of Nb(=NtBu)Cp(NMe ₂ ) ₂ (2 g, 6.3 mmol) (purchased from Air Liquide Advanced Materials Inc.) in 30 mL of toluene at -78°C, tertiary butanol (0.93 g, 12.6 mmol was added ) (manufactured by Sigma-Aldrich Corporation). After the mixture was stirred at room temperature (about 25°C) for 12 hours, the solvent was removed under vacuum to obtain a yellow oil. This material was then purified by distillation at 25 mTorr up to 100°C to obtain 2.0 g (yield 84.6%) of a yellow oil. The product was characterized by NMR ¹ H (π, ppm, C ₆ D ₆ ): 6.17 (s, 5H), 1.32 (s, 18H), 1.21 (s, 9H).

The purified product was subjected to open-cup TGA analysis (measured using a model TGA/DSC 1 STARe System manufactured by Mettler Toledo Co., Ltd.) at a temperature rise rate of 10°C/min in the atmosphere with a nitrogen flow of 200 mL/min. The results were obtained 0.6% residual caking remains. The results are shown in Figure 2. Figure 2 is a thermogravimetric analysis (TGA) graph showing the weight percentage as the temperature increases. Through differential scanning calorimetry of the product (DSC, manufactured by Mettler Toledo Company, model: DSC 1 STARe System (measured using ME-51140728)), the melting onset temperature (34.5°C) and decomposition onset temperature (285.1°C) were obtained . The results are shown in Figure 5 .

Figure 10 shows the compound produced in Example 2, namely bis(tertiary butyloxy)(tertiary butylcarboxylimide)cyclopentadienylniobium, Nb(=NtBu)(Cp)(OtBu) _2. Ozone-based ALD window.

<Example 3> Synthesis of Nb(=NtBu)(Cp)(OsBu) ₂ and bis(secondary butoxy)(tertiary butylcarboxylimide)cyclopentadienyl niobium

To a solution of Nb(=NtBu)Cp(NMe ₂ ) ₂ (2 g, 6.3 mmol) (purchased from Air Liquide Advanced Materials Inc.) in 30 mL of toluene at -78°C, was added secondary butanol (0.93 g, 12.6 mmol). ) (manufactured by Sigma-Aldrich Corporation). After the mixture was stirred at room temperature (about 25°C) for 12 hours, the solvent was removed under vacuum to obtain a yellow oil. This material was then purified by distillation at 25 mTorr up to 125°C to obtain 1.75 g (yield 74%) of a yellow oil. The product was analyzed by NMR ¹ H (π, ppm, C ₆ D ₆ ): 6.19 (s, 5H), 4.49 (m, 2H), 1.61 (m, 2H), 1.49 (m, 2H), 1.31 (d, 3H), 1.26 (d, 3H), 1.18 (s, 9H), 0.99 (t, 6H) for characterization.

The purified product was subjected to open-cup TGA analysis (measured using a model TGA/DSC 1 STARe System manufactured by Mettler Toledo Co., Ltd.) at a temperature rise rate of 10°C/min in the atmosphere with a nitrogen flow of 200 mL/min. The results were obtained 1.3% residual caking remains. The results are shown in Figure 3. Figure 3 is a thermogravimetric analysis (TGA) graph showing the weight percentage as the temperature increases. Through differential scanning calorimetry of the product (DSC, manufactured by Mettler Toledo Company, model: DSC1 STARe System (measured using ME-51140728)), the decomposition onset temperature (318.6°C) was obtained. The results are shown in Figure 6 .

<Synthesis Example 1> Compound V(=NtBu)(Cp)(OEt) ₂ can be synthesized by the following method.

By dropping method, ethanol was added to the solution of V(=NtBu)(Cp)(NMe ₂ ) ₂ in toluene at -78°C. After the mixture was stirred at room temperature for 12 hours, the solvent was removed in vacuo. The material is then purified by distillation or sublimation to obtain the final product.

<Synthesis Example 2> Compound Ta(=NtBu)(Cp)(OEt) ₂ can be synthesized by the following method.

By dropping method, ethanol was added to the solution of Ta(=NtBu)(Cp)(NMe ₂ ) ₂ in toluene at -78°C. After the mixture was stirred at room temperature for 12 hours, the solvent was removed in vacuo. The material is then purified by distillation or sublimation to obtain the final product.

Figure 7 shows bis(dimethylamide)(tertiary butylamide)cyclopentadienylniobium, Nb(=NtBu)( Thermogravimetric analysis (TGA, measured using a model TGA/DSC 1 STARe System manufactured by Mettler Toledo Company) graph of the mass percentage of Cp)(NMe ₂ ) ₂ as the temperature increases.

Table 1 below shows a comparison of the vapor pressures of the disclosed compounds and several existing compounds.

[Table 1] compound At a temperature of 133.3 Pa Nb(=NtBu)Cp(OEt) ₂ 100℃ Nb(=NtBu)Cp(OtBu) ₂ 105℃ Nb(=NtBu)Cp(OsBu) ₂ 119℃ Nb(=NtBu)Cp(NMe ₂ )(OtBu) 106℃ Nb(=NtBu)Cp(NMe ₂ ) ₂ 117℃ Nb(Cp) ₂ (iPr-amd) ₂ 170℃

without

[Fig. 1] Heat representing the weight percentage of bis(ethoxy)(tertiary butylcarboxylimide)cyclopentadienylniobium and Nb(=NtBu)(Cp)(OEt) ₂ as the temperature rises Gravimetric analysis (TGA) graph. [Figure 2] shows the weight percentage of bis(tertiary butyloxy)(tertiary butylcarboxylimide)cyclopentadienylniobium and Nb(=NtBu)(Cp)(OtBu) ₂ as the temperature increases Thermogravimetric analysis (TGA) curve graph. [Figure 3] shows the weight percentage of bis(secondary butoxy)(tertiary butylcarboxylimide)cyclopentadienylniobium and Nb(=NtBu)(Cp)(OsBu) ₂ as the temperature increases Thermogravimetric analysis (TGA) curve graph. [Figure 4] Differential scanning calorimetry (DSC) of bis(ethoxy)(tertiary butylcarboxylimide)cyclopentadienylniobium, Nb(=NtBu)(Cp)(OEt) ₂ . [Figure 5] Differential scanning calorimetry (DSC) of bis(tertiary butyloxy)(tertiary butylcarboxylimide)cyclopentadienylniobium, Nb(=NtBu)(Cp)(OtBu) ₂ . [Figure 6] Differential scanning calorimetry (DSC) of bis(secondary butoxy)(tertiary butylcarboxylimide)cyclopentadienylniobium, Nb(=NtBu)(Cp)(OsBu) ₂ . [Fig. 7] shows the relationship between bis(dimethylamide)(tertiary butylamide)cyclopentadienylniobium and Nb(=NtBu)(Cp)(NMe ₂ ) ₂ as the temperature increases. Mass percentage versus thermogravimetric analysis (TGA) graph. [Fig. 8] shows the ozone-based ALD window of bis(ethoxy)(tertiary butylcarboxylimide)cyclopentadienylniobium, Nb(=NtBu)(Cp)(OEt) ₂ . [Fig. 9] Film coating images (SEM measurement) of patterned wafers of Nb ₂ O ₅ films formed by depositing Nb (=NtBu) (Cp) (OEt) ₂ at 250°C and 300°C. [Fig. 10] Ozone-based ALD window showing bis(tertiary butyloxy)(tertiary butylcarboxylimide)cyclopentadienylniobium, Nb(=NtBu)(Cp)(OtBu) ₂ .

Claims (17)

A compound represented by the following formula (1) for forming a metal-containing film by evaporation: (In formula (1), M is V or Nb, R ¹ , R ² and R ³ are each independently H or a C1-C10 alkyl group, L is an olefin structure derived from substituted or unsubstituted C3 or above, C4 For the ligands of the above diene structures, cyclic diene structures with C5 or above, or condensed aromatic ring structures, the value of e is 0 or 1; or, M is Ta, and R ¹ , R ² and R ³ are each independently H. Or C1～C10 alkyl group, L is a ligand derived from a substituted or unsubstituted C3 or above olefin structure, C4 or above diene structure, C6 or above cyclodiene structure or condensed aromatic ring structure, the value of e is 0 or 1). The compound of claim 1, wherein M is V or Nb, and L is a ligand derived from substituted or unsubstituted cyclopentadiene. For example, the compound of claim 1 or 2, wherein the value of e is 1. The compound of any one of claims 1 to 3, wherein M is Nb. The compound according to any one of claims 1 to 4, wherein R ¹ is tertiary butyl. The compound of any one of claims 1 to 5, wherein R ² and R ³ are independently ethyl, tertiary butyl or secondary butyl. For example, the compound of claim 1 is represented by the following general formula (1-1): (In formula (1-1), M is V or Nb, R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently H, C1 to C10 alkyl group, halogen atom, alkylsilyl group, alkyl group, etc. Germanium group, alkyl amide group or alkyl silyl amide group, R ¹ , R ² and R ³ are synonymous with the formula (1)). For example, the compound of claim 1 is represented by the following general formula (1-2): (In formula (1-2), M is V, Nb or Ta, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently H, C1 to C10 alkyl or halogen atoms, R ¹ , R ² and R ³ are synonymous with the formula (1)). For example, the compound of claim 1 is represented by the following general formula (1-3): (In formula (1-3), M is V, Nb or Ta, R ¹⁶ and R ¹⁷ are independently H, C1 to C10 alkyl or halogen atom, R ¹ and R ² are synonymous with the formula (1)) . For example, the compound of claim 1 is represented by the following general formula (1-4): (In formula (1-4), M is V, Nb or Ta, R ¹⁸ , R ¹⁹ and R ²⁰ are independently H, C1 to C10 alkyl or halogen atom, R ¹ , R ² and R ³ are the same as the Synonymous with formula (1)). A method for forming a metal-containing film, which includes the following steps: Introduction step: introducing the compound according to any one of claims 1 to 10 into a reactor with a substrate inside; and Depositing step: depositing at least part of the compound on the substrate. The method for forming a metal-containing film according to claim 11, wherein in the introducing step, a co-reactant is further introduced into the reactor. The method for forming a metal-containing film of claim 12, wherein the co-reactant is selected from the group consisting of O ₂ , O ₃ , H ₂ O, H ₂ O ₂ , NO, N ₂ O, NO ₂ , trimethyl phosphate, the A group composed of oxygen free radicals and their mixtures. In the method for forming a metal-containing film according to any one of claims 11 to 13, the deposition step is performed by an atomic layer deposition method. The method for forming a metal-containing film according to any one of claims 11 to 14, wherein the substrate contains cathode active material powder. The method for forming a metal-containing film according to any one of claims 11 to 14, wherein the substrate contains cathode active material powder, conductive carbon and binder material. A method for producing a compound according to claim 1, which includes mixing a precursor compound represented by the following formula (i) with an alcohol represented by the following formula (α-1) and an alcohol represented by the following formula (α-2) Steps for at least one of the reactions: (In the formula (i), M, R ¹ , L and e are synonymous with the formula (1), and R ^a and R ^b are each independently a C1 to C5 alkyl group); (In the formulas (α-1) and (α-2), R ² and R ³ are synonymous with the formula (1)).