KR20090108552A - Preparation of metal oxide thin film via cyclic cvd or ald - Google Patents

Abstract

PURPOSE: A manufacture of a metal oxide thin film using a cyclic CVD(Chemical Vapor Deposition) or ALD(Atomic Layer Deposition) is provided to form a metal oxide thin film at a low deposition temperature. CONSTITUTION: A metal ketoiminate is introduced inside a deposition chamber. The chemically absorbed metal ketoiminate is deposited on a heated substrate. A non-reaction metal ketoiminate and an arbitrary by-product are removed by purging the deposition chamber. An oxygen-contained supply source is introduced inside the heated substrate. The arbitrary by-product is removed by purging the deposition chamber. A cyclic deposition process is repeated until a metal oxide film of desired thickness is formed.

Description

Fabrication of Metal Oxide Thin Films by Periodic CD or ALD TECHNICAL FIELD

The present invention relates to a periodic deposition method for forming a metal oxide film on a substrate.

High dielectric constant (high k) thin films, such as SrTiO ₃ (STO) and Ba (Sr) TiO ₃ (BST), have been extensively studied as one of the promising capacitor materials for next generation dynamic random access memory (DRAM) devices. For this use, very conformal deposition in terms of film thickness and composition is needed for three-dimensional (3-D) capacitor structures.

Recently, atomic layer deposition (ALD) processes have been developed to meet these requirements using a variety of raw materials. ALD is one of the most promising technologies based on its unique self-limiting deposition mechanism. In general, ALD may exhibit low deposition temperature, good step coverage for high aspect ratio features, good thickness uniformity, and accurate thickness control by layer-by-layer film deposition. .

Plasma enhanced ALD (PEALD) has also been developed due to its advantages such as higher deposition rates and lower deposition temperatures while maintaining the benefits of ALD.

For precursor materials, for example, an STO thin film may be formed of Sr bis (2,2,6,6-tetramethyl-3,5-heptanedionato) as an Sr precursor, ie (Sr (thd) ₂ ), TTIP as Ti precursor (Ti-tetraisopropoxide) and can be deposited using O ₃ , O ₂ plasma or H ₂ O vapor as oxidant. With regard to Sr precursors in particular, although Sr (thd) ₂ and some other Sr precursors have been extensively studied, such precursors still have limitations such as excessively low vapor pressure, thermal decomposition at low temperatures, and the like.

Thus, compatibility with respect to physical and chemical properties such as melting point, solubility, vaporization behavior, and reactivity to semi-fabricated semiconductor surfaces, which requires the development of suitable Group 2 or 4 precursors and corresponding deposition methods, is essential. There is still a need to find group 2 and 4 complexes with similar ligands to have. As a result, the Group 2 and Group 4 complexes described above can be dissolved in a solvent and transferred to the reaction chamber to deposit a multicomponent metal oxide film for DRAM applications.

Summary of the Invention

The present invention includes the steps of introducing a metal ketoiminate into a deposition chamber and depositing the metal ketoiminate on a heated substrate; Purging the deposition chamber to remove unreacted metal ketoiminate and any byproducts; Introducing an oxygen containing source into the heated substrate; Purging the deposition chamber to remove any byproducts; And repeating the periodic deposition process until a film of a desired thickness is formed, wherein the periodic deposition method is for forming a metal oxide film on a substrate.

The present invention describes a method of making a metal or multicomponent metal oxide film, such as strontium oxide, titanium oxide or strontium titanate, which can be used, for example, in the manufacture of semiconductor devices. The method disclosed herein provides a metal or multicomponent metal oxide film having a dielectric constant substantially higher than that of conventional thermal silicon oxide, silicon nitride or zirconium / hafnium oxide dielectrics.

The methods disclosed herein deposit metal oxide films using cyclic chemical vapor deposition (CCVD) or atomic layer deposition (ALD) techniques. In certain embodiments, the metal oxide film is deposited through a plasma enhanced ALD (PEALD) or plasma enhanced CCVD (PECCVD) process. In this embodiment, the deposition temperature may be relatively low, such as 200 to 600 ° C., to adjust the specification of the film properties needed in DRAM or other semiconductor applications. The method disclosed herein uses a metal ketoiminate precursor and an oxygen source to form a metal oxide film.

Typical processes are described as follows:

Step 1. chemically absorbing the precursor onto the heated substrate by contacting a vapor of a metal ketoiminate precursor with the heated substrate;

Step 2. purging away any unabsorbed ketoiminate precursor and any byproducts;

Step 3. Introducing an oxygen source onto the heated substrate to react with the absorbed metal ketoiminate precursor; And

Step 4. Purge and remove any unreacted oxygen source and by-products.

In one embodiment, the keitominate precursor is selected from the group represented by the following structure:

로 이루어지는 군으로부터 선택된다.In the above formula A, M is a divalent group 2 metal including calcium, magnesium, strontium, barium. For example, R ¹ is selected from the group consisting of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, fluoroalkyl, cycloaliphatic groups, and aryl groups of 6 to 12 carbon atoms; R ² is selected from the group consisting of hydrogen, 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, alkoxy, cycloaliphatic groups, and aryl groups having 6 to 12 carbon atoms; R ³ is selected from the group consisting of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, fluoroalkyl, cycloaliphatic groups, and aryl groups of 6 to 12 carbon atoms; R ⁴ is a C _2-3 linear or branched alkyl bridge with or without a chiral carbon atom, whereby a 5- or 6-membered coordinated ring is formed with respect to the metal center, examples of which include Include but are not limited to-(CH ₂ ) _2- , (CH ₂ ) _3- , -CH (Me) CH _2- , -CH ₂ CH (Me)-; R ^5-6 are individually selected from the group consisting of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, fluoroalkyl, cycloaliphatic groups, and aryl groups of 6 to 12 carbon atoms, which are linked to carbon Various organic groups can be used, such as those capable of forming a ring containing oxygen or nitrogen atoms. Metal ketoiminates of formula A are preferably

It is selected from the group which consists of.

In another embodiment, the keitominate precursor is selected from the group represented by the following structural formula:

In Structural Formula B, M is a tetravalent Group 4 metal comprising titanium, zirconium or hafnium. For example, R ⁷ is selected from the group consisting of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, fluoroalkyl, cycloaliphatic groups, and aryl groups of 6 to 12 carbon atoms; R ^8-9 is selected from the group consisting of hydrogen, 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, alkoxy, cycloaliphatic groups, and aryl groups having 6 to 12 carbon atoms; R ¹⁰ is a C _2-3 linear or branched alkyl bridge with or without chiral carbon atoms, whereby a 5- or 6-membered ring is formed with respect to the metal center, examples of which are Various organic groups can be used, including, but not limited to,-(CH ₂ ) _2- , (CH ₂ ) _3- , -CH (Me) CH _2- , and -CH ₂ CH (Me)-.

The deposition methods disclosed herein can include one or more purge gases. The purge gas used to purge and remove the unreacted reactants and / or by-products is an inert gas that does not react with the precursor, which may preferably be selected from the group consisting of Ar, N ₂ , He and mixtures thereof. . Depending on the deposition method, a purge gas such as Ar is fed into the reactor at a flow rate of about 10 to 2000 sccm, for example for about 0.1 to 1000 seconds, thereby purging any unreacted material and any byproducts remaining in the chamber.

The substrate temperature in the reactor, ie the deposition chamber, may preferably be less than about 600 ° C. and more preferably less than about 500 ° C., and the process pressure is preferably from about 0.01 to about 100 Torr and more preferably from about 0.1 Torr to about It can be 5 Torr.

The oxygen source in step 3 may be an oxygen containing source selected from the group consisting of oxygen, oxygen plasma, water, water plasma, ozone, nitrogen oxides and mixtures thereof.

Each step of supplying the precursor and the oxygen source gas can be performed by varying the duration of time for supplying them to change the stoichiometric composition of the resulting metal oxide film. For multicomponent metal oxide films, ketoiminate precursors selected from structural formulas "A" or "B" can be introduced into the reaction chamber in turn in step 1.

Direct liquid delivery methods can be employed by dissolving the ketoiminate in a suitable solvent or solvent mixture to produce a solution having a molar concentration of 0.01 to 2 M, depending on the solvent or mixed solvent used. The solvent used in the present invention is any affinity solvent or mixture thereof, preferably high boiling point, including aliphatic hydrocarbons, aromatic hydrocarbons, linear or cyclic ethers, esters, nitriles, alcohols, amines, polyamines and organic amides. Solvents such as mesitylene (boiling point: 164 ° C), or N-methyl-2-pyrrolidinone (boiling point: 202 ° C), and more preferably tetrahydrofuran (THF) or N-methylpyrrolidinone (NMP Solvent mixtures consisting of a polar solvent such as) and a nonpolar solvent such as dodecane.

Plasma-generated processes include a direct plasma forming process in which plasma is formed directly in the reactor, or a remote plasma forming method in which a plasma is formed outside the reactor and fed into the reactor.

The present invention also contemplates a periodic deposition method for forming a three-component metal oxide film in which a plurality of precursors are sequentially introduced into the deposition chamber, vaporized and deposited onto a substrate under conditions for forming a film of ternary metal oxide. .

The present invention further contemplates that the resulting metal oxide film can be exposed to plasma treatment to densify the resulting multicomponent metal oxide film.

The present invention is useful as a method of depositing a metal oxide or a multicomponent metal oxide thin film used in a semiconductor device structure. Using the present invention, metal oxide films may be formed by atomic layer deposition ALD or CCVD methods, depending on the process conditions.

ALD growth proceeds by alternately exposing the substrate surface to different precursors. ALD differs from CVD in that the precursors are kept in tight separation from each other in the gas phase. In an ideal ALD window where film growth proceeds by self-limiting control of the surface reaction, the pulse length and deposition temperature of each precursor do not affect the growth rate when the surface is saturated.

The CCVD process can be performed at a higher temperature range than the ALD process, in which the precursor decomposes. CCVD differs from traditional CVD in terms of precursor separation. Each precursor is introduced sequentially and completely separated in CCVD, but in traditional CVD all reactant precursors are introduced into the reactor and induced to react with each other in the gas phase. A common feature of CCVD and traditional CVD is that they are all about the thermal decomposition of the precursors.

The present invention is also useful as a method of depositing metal oxide films using plasma enhanced ALD (PEALD) techniques to form semiconductor device structures. Metal oxide films can be prepared by CVD and typical thermal ALD; Deposition rates can be increased using PEALD, which is known to improve film properties and expand process windows.

Example 1

This example describes the CCVD deposition of SrO using Sr ketoiminate precursor, Sr { ^t BuC (O) CHC (NCH ₂ CH ₂ NMe ₂ ) Me} ₂ and O ₂ plasma dissolved in mesitylene. The deposition temperature ranged from 200 to 400 ° C. and used direct liquid injection (DLI) where a vaporizer was used to deliver the Sr precursor. The deposition chamber pressure range was about 1.5 Torr, depending on the gas flow rate. The dip tube side of the canister, which contains the Sr precursor dissolved in liquid (mesitylene), is connected to the injector valve in the DLI system, and pressurized N ₂ (about 30 psig) is connected to the canister. It was connected to the other side to push the liquid. One cycle of CCVD of SrO consisted of five steps:

1. Injection of 0.1 M solution of Sr precursor in mesitylene: Opening the injection valve for a few milliseconds will give the Sr precursor containing steam in the vaporizer.

2. Sr pulse: introducing Sr precursor vapor into the deposition chamber; The Sr precursor is chemically absorbed onto the heated substrate.

3. Ar Purge: Any unabsorbed Sr precursor is purged with Ar to remove.

4. O ₂ Plasma Pulse: O ₂ is introduced into the deposition chamber while applying radio frequency (RF) power (50 watts (W) in this case) to react with the Sr precursor absorbed on the heated substrate.

5. Ar Purge: Purge any unreacted O ₂ and byproducts with Ar to remove.

In this embodiment, an SrO film is obtained, which indicates the deposition temperature dependency of the SrO film. Injection time was 2 milliseconds, Sr pulse time was 5 seconds, Ar purge time after Sr pulse was 10 seconds, O ₂ plasma pulse time was 3 seconds, and Ar purge time after O ₂ plasma pulse was 10 seconds. Repeated for 150 cycles.

The results are shown in FIG. 3, where the ALD process window was about 320 ° C. or less.

Example 2

In this example, the SrO film was deposited through the following conditions: The injection time of the 0.1 M solution of Sr precursor, Sr { ^t BuC (O) CHC (NCH ₂ CH ₂ NMe ₂ ) Me} ₂ in mesitylene was 2 milliseconds The Sr precursor pulse time was 5 seconds, the Ar purge time after the Sr pulse was 10 seconds, the O ₂ plasma pulse time was 3 seconds, and the Ar purge time after the O ₂ plasma pulse was 10 seconds. Wafer temperature was 250 ° C. Experiments were performed for 50, 150, 250, 300 and 600 cycles respectively. The results are shown in FIG. 4, which shows a linear dependence of film thickness versus number of cycles, which is a characteristic of the ALD process.

Example 3

In this example, the SrO film was deposited through the following conditions: The injection time of the 0.1 M solution of Sr precursor, Sr { ^t BuC (O) CHC (NCH ₂ CH ₂ NMe ₂ ) Me} ₂ in mesitylene was 2 milliseconds The Ar purge time after the Sr precursor pulse was 10 seconds, the O ₂ plasma pulse time was 3 seconds, and the Ar purge time after the O ₂ plasma pulse was 10 seconds. Wafer temperature was 250 ° C. Sr pulse time was changed from 1 second to 7 seconds. The results are shown in FIG. 5, which shows a saturation curve of about 5 seconds during the Sr pulse, which suggests a typical self-limiting ALD process under these conditions.

Example 4

This example describes the ALD or CCVD deposition of SrO with Sr ketoiminate precursor dissolved in mesitylene, Sr { ^t BuC (O) CHC (NCH ₂ CH ₂ NMe ₂ ) Me} ₂ and ozone. The deposition temperature ranged from 200 to 425 ° C. and used DLI (Direct Liquid Injection) where a vaporizer was used to deliver the Sr precursor. The deposition chamber pressure range was about 1.5 Torr, depending on the gas flow rate. Connect the dip tube side of the canister, containing the Sr precursor dissolved in liquid (mesitylene), to the injector valve in the DLI system, and pressurized N ₂ (about 30 psig) to the other side of the canister to push the liquid. It was. One cycle of CCVD of SrO consisted of five steps:

1. Injection of 0.1M solution of Sr precursor in mesitylene; Opening the injection valve for a few milliseconds will supply the Sr precursor containing vapor in the vaporizer.

2. Sr pulse: introducing Sr precursor vapor into the deposition chamber; The Sr precursor is chemically absorbed onto the heated substrate.

3. Ar Purge: Any unabsorbed Sr precursor is purged with Ar to remove.

4. Ozone Pulse: Introduces ozone into the deposition chamber.

5. Ar purge: purge off any unreacted ozone and any by-products with Ar.

In this example, an SrO film was obtained, indicating the deposition temperature dependence of the resulting SrO film deposition rate. Injection time was 2 milliseconds, Sr pulse time was 5 seconds, Ar purge time after Sr pulse was 10 seconds, ozone pulse time was 5 seconds, and Ar purge time after ozone pulse was 10 seconds.

The results are shown in FIG. 6, where the ALD process window was about 340 ° C. or less.

Example 5

This example is based on the Sr ketoiminate precursor dissolved in 10% (weight) THF in dodecane, Sr { ^t BuC (O) CHC (NCH (Me) CH ₂ NMe ₂ ) Me} ₂ and SrO using ozone. ALD or CCVD deposition is described. Deposition temperatures ranged from 200 to 425 ° C. and commercial DLI (Direct Liquid Injection) systems were used to deliver the Sr precursors. The deposition chamber pressure range was about 1.5 Torr, depending on the gas flow rate. The canister's dip tube side, containing Sr precursor dissolved in 10% (weight) of THF in dodecane, was connected to the injector valve in the DLI system, and the pressurized N ₂ (about 30 psig) was connected to the other side of the canister. To push the liquid. In this case, the injector valve is always open and the liquid mixture of the Sr precursor and the solvent is vaporized through the nozzle (spray). Carrier gas assisted vaporization. One cycle of ALD or CCVD of SrO consisted of four steps:

1.Inject 0.1M solution of Sr { ^t BuC (O) CHC (NCH (Me) CH ₂ NMe ₂ ) Me} ₂ in 10% (weight) THF in dodecane to deliver Sr precursor vapor to the deposition chamber. and; The Sr precursor is chemically absorbed onto the heated substrate.

2. Ar purge: purge any unabsorbed Sr precursor with Ar.

3. Ozone Pulse: Introduces ozone into the deposition chamber.

4. Ar purge: purge any unreacted ozone and any by-products with Ar.

In this example, an SrO film was obtained, indicating the deposition temperature dependence of the resulting SrO film thickness. The injection time of the Sr pulse time was 5 seconds, the Ar purge time was 5 seconds after the Sr pulse, the ozone pulse time was 5 seconds, and the Ar purge time after the ozone pulse was 5 seconds.

The results are shown in FIG. 7, where the ALD process window was about 320 ° C. or less.

Example 6

In this example, a direct liquid injection vaporizer system was monitored while vaporizing a strontium precursor, Sr { ^t BuC (O) CHC (NCH ₂ CH ₂ NMe ₂ ) Me} ₂ , dissolved in a solvent through a heated injector. In this case, the injector was heated to 185 ° C., the flow rate of the carrier gas was 500 sccm of the helium gas, and the precursor-solvent mass flow rate was 1 g / min. The pressure monitor was placed straight in the carrier gas stream, in front of the injector.

The results in FIG. 8 show that with a combined solvent of 10% (weight) of THF in dodecane, a very stable back pressure is obtained over an operating time of about 3 hours. In contrast, the same concentration of strontium precursor dissolved in mesitylene shows a continuous increase in back pressure as additional precursor flows through the injector system. The combined effect of the higher boiling point of dodecane and the additional solubility obtained by adding THF allows stable injector performance for the duration of this flow test.

1 is a thermogravimetric analysis of Sr { ^t BuC (O) CHC (NCH ₂ CH ₂ NMe ₂ ) Me} ₂ (solid line) and Ti {MeC (O) CHC (NCH ₂ CH ₂ O) Me} ₂ (dashed line) A graph according to a differential scanning calorimeter (TGA / DSC) is shown, which shows that the two complexes described above are compatible due to their very similar vaporization behavior.

FIG. 2 shows Sr { ^t BuC (O) CHC (NCH (Me) CH ₂ NMe ₂ ) Me} ₂ (solid line) and Ti {MeC (O) CHC (NCH (Me) CH ₂ O) Me} ₂ (dashed line) A graph according to TGA / DSC is shown, which shows that the two complexes above show affinity due to their same melting point and similar vaporization behavior.

FIG. 3 shows the temperature dependence of PEALD depositing SrO using Sr { ^t BuC (O) CHC (NCH ₂ CH ₂ NMe ₂ ) Me} ₂ and O ₂ plasma.

4 shows the SrO thickness dependence obtained using the number of deposition cycles at a temperature of 250 ° C. via PEALD using Sr { ^t BuC (O) CHC (NCH ₂ CH ₂ NMe ₂ ) Me} ₂ and O ₂ plasma.

FIG. 5 shows the SrO thickness dependence obtained using Sr { ^t BuC (O) CHC (NCH ₂ CH ₂ NMe ₂ ) Me} ₂ pulse time at 250 ° C. via PEALD.

6 shows the temperature dependence of thermal ALD for depositing SrO using Sr { ^t BuC (O) CHC (NCH ₂ CH ₂ NMe ₂ ) Me} ₂ and ozone.

FIG. 7 shows the temperature dependence of thermal ALD for depositing SrO using Sr { ^t BuC (O) CHC (NCH (Me) CH ₂ NMe ₂ ) Me} ₂ and ozone.

8 demonstrates direct liquid injection stability through back pressure monitoring in front of the injector orifice. A) 0.1 M strontium precursor Sr { ^t BuC (O) CHC (NCH (Me) CH ₂ NMe ₂ ) Me} ₂ dissolved in 10% (weight) tetrahydrofuran in dodecane, and B) mesitylene 0.1 M strontium precursor Sr { ^t BuC (O) CHC (NCH (Me) CH ₂ NMe ₂ ) Me} ₂ .

Claims (36)

A periodic deposition method for forming a metal oxide film on a substrate, Introducing a metal ketominate into the deposition chamber and depositing a chemically absorbed metal ketomidate on the heated substrate; Purging the deposition chamber to remove unreacted metal ketoiminate and any byproducts; Introducing an oxygen containing source into the heated substrate; Purging the deposition chamber to remove any byproducts; And Repeating the periodic deposition process until a metal oxide film of desired thickness is formed. The process of claim 1 wherein the metal ketoiminate is selected from the group represented by the following formula (A) or (B):

[In Formula A, M is a divalent group 2 metal selected from the group consisting of calcium, magnesium, strontium and barium; R ¹ is selected from the group consisting of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, fluoroalkyl, cycloaliphatic groups, and aryl groups having 6 to 12 carbon atoms; R ² is selected from the group consisting of hydrogen, 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, alkoxy, cycloaliphatic groups, and aryl groups having 6 to 12 carbon atoms; R ³ is selected from the group consisting of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, fluoroalkyl, cycloaliphatic groups, and aryl groups of 6 to 12 carbon atoms; R ⁴ is preferably a C _2-3 linear or branched alkyl bridge, with or without chiral carbon atoms, of 2 or 3 carbon atoms, whereby a 5 or 6 membered ring is formed relative to the metal center Become; R ^5-6 are individually selected from the group consisting of alkyl, fluoroalkyl, cycloaliphatic groups, and aryl groups having 6 to 12 carbon atoms, having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, To form a ring comprising carbon, oxygen or nitrogen atoms; or

[In Formula B, M is a tetravalent Group 4 metal selected from the group consisting of titanium, zirconium and hafnium; R ⁷ is selected from the group consisting of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, fluoroalkyl, cycloaliphatic groups, and aryl groups of 6 to 12 carbon atoms; R ^8-9 is selected from the group consisting of hydrogen, 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, alkoxy, cycloaliphatic groups, and aryl groups having 6 to 12 carbon atoms; R ¹⁰ is a C _2-3 linear or branched alkylene bridge with or without chiral carbon atoms, whereby a five or six membered ring is formed relative to the metal center]. The method of claim 2, wherein the metal ketoimilate is delivered via direct liquid delivery by dissolving the ketoiminate in a solvent or solvent mixture to produce a solution having a molar concentration of 0.01 to 2M. 4. The process of claim 3 wherein the solvent is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, linear or cyclic ethers, esters, nitriles, alcohols, amines, polyamines, organic amides and mixtures thereof. The process of claim 4 wherein the solvent is selected from the group consisting of tetrahydrofuran (THF), mesitylene, dodecane, N-methylpyrrolidinone (NMP) and mixtures thereof. 6. The method of claim 5 wherein the solvent is a mixture consisting of tetrahydrofuran (THF) and dodecane. The method of claim 6, wherein the weight percent of tetrahydrofuran (THF) is 1-90%. The method of claim 1 wherein the metal oxide is strontium oxide. The method of claim 1 wherein the metal oxide is titanium oxide. The method of claim 1, wherein the periodic deposition process is a periodic chemical vapor deposition process. The method of claim 1, wherein the periodic deposition process is an atomic layer deposition process. The method of claim 1 wherein the pressure in the deposition chamber is between 50 mtorr and 100 torr and the temperature in the deposition chamber is less than 600 ° C. The method of claim 1 wherein the oxygen containing source is selected from the group consisting of oxygen, oxygen plasma, water, water plasma, ozone, nitric oxide and mixtures thereof. The method of claim 1, wherein the resulting metal oxide film is exposed to a rapid thermal annealing (RTA) process or plasma treatment, thereby densifying the resulting metal oxide film. The method of claim 1, wherein the metal ketoiminate is Sr { ^t BuC (O) CHC (NCH ₂ CH ₂ NMe ₂ ) Me} ₂ , Sr { ^t BuC (O) CHC (NCH ₂ CH ₂ NEt ₂ ) Me} ₂ , Sr { ^t BuC (O) CHC (NCH (Me) CH ₂ NMe ₂ ) Me} ₂ , and Sr { ^t BuC (O) CHC (NCH (Me) CH ₂ NEt ₂ ) Me} ₂ How to be. A periodic deposition method for forming a three component metal oxide film, A number of precursors are sequentially introduced into the deposition chamber, vaporized, and deposited onto the substrate under conditions to form a three-component metal oxide film, Using the first metal ketoiminate as the first precursor, Using an oxygen-containing source, Using a second metal ketoiminate as the second different precursor, Periodic deposition method using an oxygen containing source. 17. The method of claim 16, wherein one of the ketoiminates is selected from the group represented by formula A or formula B below:

[In Formula A, M is a divalent group 2 metal selected from the group consisting of calcium, magnesium, strontium and barium; R ¹ is selected from the group consisting of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, fluoroalkyl, cycloaliphatic groups, and aryl groups having 6 to 12 carbon atoms; R ² is selected from the group consisting of hydrogen, 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, alkoxy, cycloaliphatic groups, and aryl groups having 6 to 12 carbon atoms; R ³ is selected from the group consisting of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, fluoroalkyl, cycloaliphatic groups, and aryl groups of 6 to 12 carbon atoms; R ⁴ is a C _2-3 linear or branched alkyl bridge with or without chiral carbon atoms, whereby a five or six membered ring is formed relative to the metal center; R ^5-6 are individually selected from the group consisting of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, fluoroalkyl, cycloaliphatic groups, and aryl groups of 6 to 12 carbon atoms, which are linked to carbon , May form a ring containing an oxygen or nitrogen atom; or

[In Formula B, M is a tetravalent Group 4 metal selected from the group consisting of titanium, zirconium and hafnium; R ⁷ is selected from the group consisting of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, fluoroalkyl, cycloaliphatic groups, and aryl groups of 6 to 12 carbon atoms; R ^8-9 is selected from the group consisting of hydrogen, 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, alkoxy, cycloaliphatic groups, and aryl groups having 6 to 12 carbon atoms; R ¹⁰ is a C _2-3 linear or branched alkylene bridge with or without chiral carbon atoms, whereby a five or six membered ring is formed relative to the metal center]. 18. The method of claim 17, wherein the metal ketoiminate is delivered via direct liquid delivery by dissolving the ketoiminate in a solvent or solvent mixture to produce a solution having a molar concentration of 0.01 to 2M. 19. The process of claim 18, wherein the solvent is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, linear or cyclic ethers, esters, nitriles, alcohols, amines, polyamines, organic amides, and mixtures thereof. 20. The method of claim 19, wherein the solvent is selected from the group consisting of tetrahydrofuran (THF), mesitylene, dodecane, N-methylpyrrolidinone (NMP), and mixtures thereof. The method of claim 16, wherein the metal oxide is strontium titanate. The method of claim 16, wherein the periodic deposition process is a periodic chemical vapor deposition process. The method of claim 16, wherein the periodic deposition process is an atomic layer deposition process. The method of claim 16, wherein the pressure in the deposition chamber is between 50 mtorr and 100 torr and the temperature in the deposition chamber is less than 500 ° C. 18. 17. The method of claim 16, wherein the oxygen containing source is selected from the group consisting of oxygen, oxygen plasma, water, water plasma, ozone, nitrogen oxides, and mixtures thereof. The method of claim 16, wherein the resulting three-component metal oxide film is exposed to a rapid thermal annealing process or a plasma treatment to densify the resulting multi-component metal oxide film. The method of claim 16, wherein the metal ketoimilate of formula A is Sr { ^t BuC (O) CHC (NCH ₂ CH ₂ NMe ₂ ) Me} ₂ , Sr { ^t BuC (O) CHC (NCH ₂ CH ₂ NEt ₂ ) Me} ₂ , Sr { ^t BuC (O) CHC (NCH (Me) CH ₂ NMe ₂ ) Me} ₂ , and Sr { ^t BuC (O) CHC (NCH (Me) CH ₂ NEt ₂ ) Me} ₂ Selected from the group, wherein the ketoiminate of formula B is Ti {MeC (O) CHC (NCH ₂ CH ₂ O) Me} ₂ and Ti {MeC (O) CHC (NCH (Me) CH ₂ O) Me} ₂ The method is selected from the group consisting of. A periodic deposition method for forming a multicomponent metal oxide film, A number of precursors are sequentially introduced into the deposition chamber, vaporized, and deposited onto the substrate under conditions to form a multicomponent metal oxide film, To prepare a solution use at least two metal ketoiminates dissolved in a solvent or solvent mixture, Periodic deposition method using an oxygen containing source. 29. The method of claim 28, wherein the at least two metal ketoimilates comprise metal ketoiminates represented by formula A and other metal ketoiminates represented by formula B and the solutions each have a molar concentration of 0.01 to 2M; The formulas A and B are defined as follows:

[In Formula A, M is a divalent group 2 metal selected from the group consisting of calcium, magnesium, strontium and barium; R ¹ is selected from the group consisting of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, fluoroalkyl, cycloaliphatic groups, and aryl groups having 6 to 12 carbon atoms; R ² is selected from the group consisting of hydrogen, 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, alkoxy, cycloaliphatic groups, and aryl groups having 6 to 12 carbon atoms; R ³ is selected from the group consisting of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, fluoroalkyl, cycloaliphatic groups, and aryl groups of 6 to 12 carbon atoms; R ⁴ is a C _2-3 linear or branched alkyl bridge with or without chiral carbon atoms, whereby a five or six membered ring is formed relative to the metal center; R ^5-6 are individually selected from the group consisting of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, fluoroalkyl, cycloaliphatic groups, and aryl groups of 6 to 12 carbon atoms, which are linked to carbon , May form a ring containing an oxygen or nitrogen atom; or

[In Formula B, M is a tetravalent Group 4 metal selected from the group consisting of titanium, zirconium and hafnium; R ⁷ is selected from the group consisting of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, fluoroalkyl, cycloaliphatic groups, and aryl groups of 6 to 12 carbon atoms; R ^8-9 is selected from the group consisting of hydrogen, 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, alkyl, alkoxy, cycloaliphatic groups, and aryl groups having 6 to 12 carbon atoms; R ¹⁰ is a C _2-3 linear or branched alkylene bridge with or without chiral carbon atoms, whereby a five or six membered ring is formed relative to the metal center]. 30. The method of claim 29, wherein the solution of metal ketoiminate is delivered via direct liquid injection. The method of claim 29 wherein the solvent is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, linear or cyclic ethers, esters, nitriles, alcohols, amines, polyamines, organic amides, and mixtures thereof. 32. The method of claim 31, wherein the solvent is selected from the group consisting of tetrahydrofuran (THF), mesitylene, dodecane, N-methylpyrrolidinone (NMP), and mixtures thereof. 29. The method of claim 28, wherein the multicomponent metal oxide is strontium titanate. 29. The method of claim 28, wherein the periodic deposition process is a periodic chemical vapor deposition process. 30. The method according to claim 29, wherein the metal ketoimilate of formula A is Sr { ^t BuC (O) CHC (NCH ₂ CH ₂ NMe ₂ ) Me} ₂ , Sr { ^t BuC (O) CHC (NCH ₂ CH ₂ NEt ₂ ) Me} ₂ , Sr { ^t BuC (O) CHC (NCH (Me) CH ₂ NMe ₂ ) Me} ₂ , and Sr { ^t BuC (O) CHC (NCH (Me) CH ₂ NEt ₂ ) Me} ₂ Selected from the group. 30. The method according to claim 29, wherein the metal ketoimilate of formula B is selected from Ti {MeC (O) CHC (NCH ₂ CH ₂ O) Me} ₂ and Ti {MeC (O) CHC (NCH (Me) CH ₂ O) Me}. The method is selected from the group consisting of ₂ .

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