KR20090070399A - Method of fabricating self-assembly multi-molecular layer - Google Patents

Abstract

A method for manufacturing a self assembly multilayer molecular layer is provided to stabilize the multilayer molecular layer by chemically coupling a metal hydroxide monolayer between the self assembly organic monolayer. A self assembly organic single molecule layer is formed on a surface of a substrate by using an MLD(Molecular Layer Deposition) method. The substrate is a metal substrate, a metal oxide substrate, a semiconductor substrate, or a glass substrate. The substrate is processed with O3. A terminal group of the self assembly organic monolayer is substituted for -OH or -COOH. A metal hydroxide monolayer is formed on the self assembly organic monolayer by reacting a metal precursor with an atomic layer deposition method.

Description

Manufacturing method of self-assembled multilayer molecular membrane {METHOD OF FABRICATING SELF-ASSEMBLY MULTI-MOLECULAR LAYER}

The present invention relates to a method for producing a self-assembled multilayer molecular film, and more particularly, to produce a high quality multilayered molecular film within a short time, and that a metal hydroxide monolayer is bonded by chemical bonds rather than physically between self-assembled organic monolayers. The present invention relates to a method for producing a self-assembled multilayer molecular membrane which can be more stabilized.

In a semiconductor device or a display device, a thin film is very important technically to form a thin film or an electrode constituting each, and is uniformly formed at a thickness level of several tens to several tens of nm according to the development of technology.

In general, Self-Assembled Monolayers (SAMs) are molecules that have relatively long alkyl groups and functional groups that can covalently bond by interacting with the substrate surface at their ends. It is a monolayer that is uniformly aligned on the surface of the substrate using a self-assembly phenomenon in which two of them are aligned in two dimensions.

The molecules forming the self-assembled monolayer are adsorbed and bonded to the surface of the substrate through a functional group, and the alkyl groups are aligned in two dimensions by hydrophobic attraction with each other to form a self-assembled monolayer.

When the monomolecular film is prepared by the above method, the film formation process can be controlled at the molecular level, and the functional groups of the molecules forming the self-assembled monomolecular film can be selectively changed in various ways, and the control thereof is also possible. It is strong, so the membrane is very stable and can be easily removed if desired.

Self-assembled monolayers with these characteristics are nanopatterning, chemical and biosensor, nanotribology, surface modification, and nano for the manufacture of semiconductors and electronic devices. It has been applied to various fields such as electromechanical systems (NEMS) and microelectromechanical systems (MEMS).

Currently, self-assembled monomolecular film production is mainly used to form on the surface of the substrate in the liquid phase. However, at present, manufacturing processes such as semiconductor devices are mostly performed by a gas phase process, and there are many problems in applying a method of manufacturing a self-assembled monolayer in a conventional liquid phase to a semiconductor manufacturing process.

Therefore, the present inventors have found that the use of molecular layer growth technology in the gas phase can produce a high quality self-assembled multilayer molecular film at a very high speed and conducted various studies.

The inventors have formed a TiO ₂ atomic layer by using atomic layer deposition (Atomic Layer Deposition) on the substrate through the Republic of Korea Patent Publication Nos. 2005-57806 and 2007-84683, and the molecular layer deposition method (Molecular Layer Deposition) A method of forming a self-assembled monomolecular film by gas phase reaction of an organic material such as a surfactant by using the present invention has been proposed.

As a result of applying multilayer molecular films (TiO ₂ / SAMs) prepared in this manner as a dielectric film of a semiconductor device, it was confirmed that leakage current was not suitable for use as an insulating film. Furthermore, in order to use it as an insulating film, the thickness should be at least 100 nm or more, and the process time was also unsatisfactory because the molecular layer deposition time was over 1 minute.

Therefore, the inventors conducted further studies to limit the vapor pressure ratio between the source gas and water during atomic layer deposition and molecular layer deposition. As a result, the formation time of the self-assembled monomolecular film was performed within 5 seconds. The present invention was completed by confirming that a metal hydroxide rather than a self-assembled monomolecular layer can increase the bonding strength and solve the leakage current problem.

It is an object of the present invention to prepare a high quality multilayer molecular film in a short time, and the self-assembled multilayer molecular film in which the metal hydroxide monomolecular layer is bonded by a chemical bond, not physically, between the self-assembled organic monomolecular film to stabilize the multi-layered molecular film. It is to provide a manufacturing method.

In order to achieve the above object, the present invention

(S1) forming a self-assembled organic monomolecular film on the surface of the substrate by vapor phase reaction using Molecular Layer Deposition (MLD);

(S2) treating the substrate with O ₃ to replace the terminal group of the self-assembled organic monomolecular film with -OH or -COOH; And

(S3) forming a metal hydroxide monomolecular layer by reacting a metal precursor on the self-assembled organic monomolecular film by atomic layer deposition (ALD);

Provided is a method for producing a self-assembled multilayer molecular film, which is repeatedly performed using the above steps (S1) to (S3) as one cycle.

The method for producing a self-assembled multilayer molecular film according to the present invention can produce a high quality multilayered molecular film within a short time, and the metal hydroxide monomolecular layer is bonded by chemical bonds rather than physically between the self-assembled organic monomolecular films to stabilize the multi-layered molecular film. Can be.

The self-assembled multi-layered molecular film is manufactured by nano patterning, chemical sensor and bio sensor, nano trilogy, surface modification, nanoelectromechanical system (NEMS), microelectromechanical system (MEMS), It can be applied to various fields such as volatile memory.

In the method for manufacturing a self-assembled multilayer molecular film according to the present invention, a self-assembled organic monolayer is formed through molecular layer deposition (MLD) and a metal hydroxide monolayer is formed through atomic layer deposition (ALD). This is done by repeating the steps.

The self-assembled multi-layered molecular film is repeated until the required thickness is obtained by one cycle of the following steps (S1) to (S3):

(S1) forming a self-assembled organic monomolecular film on the surface of the substrate by vapor phase reaction using molecular layer deposition (MLD);

(S2) treating the substrate with O ₃ to replace the terminal group of the self-assembled organic monomolecular film with -OH or -COOH; And

(S3) forming a metal hydroxide monolayer by reacting a metal precursor on the self-assembled organic monolayer by atomic layer deposition (ALD).

Hereinafter, the specific manufacturing method will be described in more detail at each step.

First, in (S1), a self-assembled organic monomolecular film is formed on the substrate surface by vapor phase reaction using molecular layer deposition (MLD).

The substrate is not limited in the present invention, and may be any substrate used in the semiconductor field. Typically, a metal substrate, a metal oxide substrate, a semiconductor substrate, or a glass substrate is possible.

The metal substrate includes at least one metal selected from the group consisting of Au, Pt, Ni, Cu, Co, Pd, Al, and combinations thereof, and the metal oxide substrate includes oxides thereof. In addition, the semiconductor substrate is Si, Ge, C, Ga, As, P, B, Zn, Se, Cd, Sn, In, SiGe, GaAs, AlGaAs, GaAsP, InAs, Sn, InAsP, InGaAs, AlAs, InP, GaP, One kind selected from the group consisting of ZnSe, CdS, ZnCdS, CdSe, and a combination thereof is possible.

Self-assembled monolayers (SAMs) are two-dimensional on the surface of the substrate, using molecules with relatively long alkyl groups and functional groups at their ends that can covalently bond with the substrate surface. By means of self-assembly aligning automatically means a monolayer (monolayer) that is uniformly aligned. The functional groups of the molecules are adsorbed and bonded to the surface of the substrate, and the alkyl groups are two-dimensionally aligned with each other by hydrophobic interaction to form a self-assembled organic monolayer. The self-assembled organic monomolecular film can control the formation process at the molecular level, and can selectively change various functional groups of the molecule, and can control it, as well as strong bonding with the substrate surface, excellent film stability, There is an advantage that can be easily removed if desired.

Thus, in the present invention, the raw material gas for forming the self-assembled organic monomolecular film includes a fatty acid including a C1 to C20 alkyl group, such as a fatty acid, an alkyltrihalosilane including a C1 to C20 alkyl group, and a C1 to C20 alkyl group. Alkyltrialkoxysilane, the alkylsiloxane containing a C1-C20 alkyl group, the alkylthiol containing a C1-C20 alkyl group, the alkylpospace containing a C1-C20 alkyl group, and a combination thereof are possible 1 type Preferably, alkyltrihalosilane of RSiCl ₃ (wherein R is a C2 to C20 alkyl group, preferably C5 to C18 alkyl group) is used.

The molecular layer deposition method (MLD) used at this time is not particularly limited in the present invention, it is performed using a known device. Such a device is composed of a gas supply device, a deposition chamber, a vacuum device, an automatic control system, a temperature control device, and the like.

Specifically, the formation of the self-assembled organic monolayer using molecular layer deposition

a1) after loading the substrate into the chamber, operate the vacuum apparatus to regulate the pressure in the chamber,

a2) controlling the temperature in the chamber while flowing purge gas into the chamber,

a3) supplying a raw material gas and H ₂ O to form a self-assembled organic monomolecular film into the chamber to form a self-assembled organic monomolecular film on the substrate,

a4) The purge gas is introduced to remove unreacted raw material gas, unreacted H ₂ O or deposition byproduct.

In order to perform the process at the high speed in the deposition of the molecular layer and to form a high quality self-assembled organic monolayer, control of process conditions is essential. These process conditions can be pressure and temperature in the chamber, type and rate of injection of the purging gas, vapor pressure of the source gas and H ₂ O.

Preferably, the pressure in the chamber during the deposition of the molecular layer is 300 to 350 mTorr, the chamber temperature is 130 to 150 ℃, the substrate temperature is adjusted to 150 to 250 ℃, preferably 200 ℃. In addition, as a purging gas, Ar or N ₂ is used and injected at 20 to 60 sccm. The process temperature and the process pressure may be the process temperature and the process pressure which are continuously maintained in subsequent processes, but the process temperature and the process pressure may be changed as necessary.

The ratio of the vapor pressure of the raw material gas and the H ₂ O into the chamber in which the temperature and the pressure are controlled is controlled to be 3: 1 to 1: 3, preferably 1: 1, wherein the vapor pressures of the raw material gas and the H ₂ O are respectively The range is 40 to 60 mTorr. If the vapor pressure of water is injected in a range less than that described in the above range, the deposition time of the self-assembled molecular film by the raw material gas is longer than 1 minute, causing an increase in the overall processing time. On the contrary, when the vapor pressure of the water is maintained in a range higher than the above range, there is a possibility that a polymerization reaction of the raw material gas may occur, and the self-assembly molecular film is difficult to form itself, so it is appropriately adjusted and used within the above range. do.

Referring to Scheme 1 below, 7-OTS (7-octenyltrichlorosilane) is used to form a self-assembled organic monolayer on the surface of a Si substrate:

Scheme 1

At this time, before forming the self-assembled organic monolayer, the substrate is pretreated to remove contaminants present on the surface of the substrate. Removal of such contaminants is possible using conventional methods. For example, after washing with distilled water and ethanol, N ₂ Purge two to three times with gas to remove contaminants present on the substrate surface.

In addition, if necessary, the surface of the substrate is UV / O ₃ treated to form an oxide film on the surface of the substrate before reforming the surface of the substrate, and -OH groups are formed on the surface of the oxide layer, thereby improving chemical reactivity (activity) during subsequent modification. It can increase.

Next, (S2) the formed self-assembled organic monomolecular film is substituted with -OH and -COOH end groups of the self-assembled organic monomolecular film using O ₃ .

The -OH or -COOH functional group facilitates the subsequent formation of the metal hydroxide monolayer, and enhances the adhesion between the formed metal hydroxide monolayer and the self-assembled organic monolayer.

At this time, the O ₃ treatment is performed by injecting 30 seconds to 1 minute while maintaining the pressure in the chamber at 50 to 100 mTorr. Referring to Scheme 2 below, it is shown that the end group of the self-assembled organic monomolecular film is substituted by O ₃ treatment:

Scheme 2

Next, in (S3), the metal precursor is reacted by atomic layer deposition (ALD) on the self-assembled organic monomolecular film activated by the O ₃ treatment to form a metal hydroxide monomolecular layer.

The metal hydroxide monolayer is an oxide containing at least one element selected from the group consisting of Al, Si, Zr, Ti, Hf, La, Ta, Mg, and combinations thereof, and is chemically bonded to a self-assembled organic monolayer. Present at a layer level thickness.

Atomic Layer Deposition (ALD) is not particularly limited in the present invention, and is carried out using a known device. Such a device is composed of a gas supply device, a deposition chamber, a vacuum device, an automatic control system, a temperature control device, and the like.

In order to form a metal hydroxide monolayer on the substrate on which the self-assembled organic monolayer is formed using the above apparatus,

c1) a metal source gas and H ₂ O are introduced in a pulse form and deposited on a substrate;

c2) reacting the metal raw material gas with a self-assembled organic monolayer to form a metal hydroxide monolayer,

c3) Purging gas is introduced to remove unreacted raw gas, unreacted H ₂ O or deposition byproducts.

At this time, the purging gas uses Ar or N ₂ .

The source gas is not limited in the present invention, and any precursor precursor capable of forming the inorganic thin film as described above may be used, and a metal compound having a high vapor pressure may be used to inject the desired precursor amount into the chamber in a short time. use. For example, the raw material gas may include alkoxide, chloride, hydroxide, oxyhydroxide, nitrate, including a metal selected from the group consisting of Al, Si, Zr, Ti, Hf, La, Ta, Mg, and combinations thereof. Groups of carbonates, acetates, oxalates and mixtures thereof are possible.

For example, a trimethyl aluminum (TMA) or the like may be used as a raw material gas for forming an Al metal hydroxide monolayer, and a trimethyl ortho silicate (TEOS) may be used as a raw material gas for forming an Si metal hydroxide monolayer. Tetramethyl silicon (TMS), tetraethyl silicon (TES), tetradimethylamino silicon (TDMAS) or tetraethylmethylamino silicon (TEMAS) are used. Tetra isopropyl zirconium (Zr (i-OPr) ₄ ), etc. may be used as a raw material gas for forming a Zr metal hydroxide monolayer, and tetra isopropyl may be used as a raw material gas for forming a Ti metal hydroxide monolayer. titanium), tetradimethyl aminoethoxide, isoprofoside titanium (Titanium isopropoxide), and the like. In addition, the raw material gas for forming the Hf metal hydroxide monolayer may be Hf ([N (CH ₃ ) (C ₂ H5)] ₃ [OC (CH ₃ ) ₃ ]) or the like, and the raw material for forming the La metal hydroxide monolayer. The gas may be triisopropyl lanthanum or the like, and raw materials for forming a Ta inorganic thin film include penta isopropyl tantalum and pentadimethylaminoethoxide tantalum. Etc., and a raw material gas for forming a Zn metal hydroxide monolayer is DEZn (Diethyl Zinc), and the like, and an organometallic precursor containing Mg may be Mg (OH) ₂ .

The temperature of the chamber is performed at a temperature of 130 to 150 ° C. in order to deposit the metal hydroxide monolayer so as not to affect the substrate. In this case, the pressure in the chamber is maintained at a process pressure of 300 to 350 mTorr. The process temperature and the process pressure may be the process temperature and the process pressure which are continuously maintained in subsequent processes, but the process temperature and the process pressure may be changed as necessary.

In this way, the ratio of the vapor pressure of the metal raw material gas and the H ₂ O to the temperature and pressure controlled chamber is adjusted to be 3: 1 to 1: 3, preferably 1: 1, wherein the vapor pressure of the metal raw material gas and the H ₂ O is adjusted. Are in the range of 40 to 60 mTorr, respectively. If the vapor pressure of water is lower than the above range, the deposition time of the metal hydroxide is increased to increase the overall process time. On the contrary, when the vapor pressure of water is excessive, there is a fear that polymerization of the metal raw material gas occurs due to reaction with the metal raw material gas.

The metal hydroxide monomolecular layer formed by the atomic layer deposition method is capable of controlling the thickness in the monoatomic layer, and a thin film having a very excellent property at low temperature is perfectly controlled and deposited by a deposition method using a perfect surface reaction.

Referring to Scheme 3 below, the self-assembled organic monolayer and the metal hydroxide monolayer are shown to be chemically bonded:

Scheme 3

When the steps (S1) to (S3) as described above are performed in one cycle, the thin film is manufactured by performing this process 1 to 1000 times. The method according to the present invention enables the production of a composite thin film on a substrate using an ALD process and a SAMs formation process.

Referring to Scheme 4 below, the self-assembled organic monomolecular film is further formed on the metal hydroxide monomolecular layer:

Scheme 4

The method according to the invention has the following advantages.

First, the thin film manufactured by the molecular layer deposition method (MLD) used in the present invention can produce a high quality organic molecular thin film at a high speed in the vapor phase by the vapor deposition method.

Second, the thin film is formed of a metal hydroxide monomolecular layer between the self-assembled organic monolayer, the bond of the self-assembled organic monolayer is more strongly connected to the superlattice thin film is a new concept of nano-thin material thin film.

Third, the formation time of the self-assembled organic monomolecular film can be reduced up to 5 seconds by controlling the vapor pressure ratio of the source gas and water during the molecular layer deposition.

This method can control the membrane formation process at the molecular level, and can selectively change the functional groups of the molecules forming the self-assembled organic monomolecular membrane, and also can control the membrane formation, and also has a strong bond with the solid substrate to ensure the stability of the membrane. It is also excellent and easy to remove if desired. Self-assembled multilayer molecular film having the above characteristics is nanopatterning, chemical sensor and biosensor, nanotribology, surface modification for semiconductor or electronic device manufacturing Applications include modification, nanoelectromechanical systems (NEMS), microelectromechanical systems (MEMS), and nonvolatile memory (Nonvolatile Memory).

In particular, in the present invention, when TMA (trimethyl aluminum) is used as the metal hydroxide monolayer, it is possible to solve the leakage current problem and reduce the film thickness of the insulating film by 10 times or less to 10 nm or less, which can be applied as a dielectric film to OTFT, and water in the deposition process. In the case of use, it is possible to form an aluminum hydroxide layer.

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited by the examples.

(Example 1)

The Si (100) substrate was washed with distilled water and ethanol, purged with N ₂ gas (2-3 times) to remove contaminants on the surface of the substrate, and then treated with O ₃ to form an oxide film.

Next, the cleaned and dried substrate was loaded into the deposition chamber and the vacuum apparatus was operated to lower the pressure to 1.0 × 10 ⁻³ torr. Subsequently, the chamber temperature was maintained at 140 ± 10 ° C and the substrate temperature was 200 ° C while flowing 50 sccm of Ar gas. Subsequently, 7-OTS (7-octenyltrichlorosilane) gas and H ₂ O were introduced into the reactor for 5 seconds on the SiO ₂ oxide film at the same vapor pressure ratio (40 mTorr) and deposited on the substrate for 5 seconds. Residual byproducts were removed. At this time, the temperature of the 7-OTS source and the H ₂ O source were 100 ° C. and room temperature, respectively, and the water was controlled by a Metiring valve.

Subsequently, the deposited 7-OTS double bond functional group was activated for 30 seconds using ozone, and then purged with Ar gas.

Next, TMA (trimethyl aluminum) and H ₂ O were introduced on the activated monolayer in a pulse form at a vapor pressure ratio of 40 mTorr for 5 seconds and deposited on the substrate, and TMA deposited by introducing Ar purging gas. And reacted to form an aluminum hydroxide film. Ar purging gas was then introduced to remove unreacted H ₂ O and reaction byproducts. At this time, the temperature of the TMA and H ₂ O was maintained at room temperature, and the steam pressure was controlled by using a metering valve.

The self-assembly multilayer molecular film was prepared by performing 40 times by defining steps 1 to 3 as the basic 1 cycle.

(Reference Example 1)

A multilayer molecular film in which TiO ₂ and 7-OTS were alternately stacked on a Si substrate was prepared in the manner described in Korean Patent Application No. 2007-84683.

Experimental Example 1

The thin film obtained in Example 1 was analyzed by X-ray Photoelectron Spectroscopy (XPS), Contact Angle Analysis (CAA) and Transmission Electron Microscopy (TEM), and the results are shown below.

XPS Analysis

1 is an XPS graph of a thin film prepared in Example 1.

Referring to FIG. 1, it can be seen that as the number of molecular layers stacked increases, the amount of carbon decreases as the amount of carbon increases, and from this, it can be seen that the deposited molecular film is formed in multiple layers.

CAA Analysis

2 is a graph showing a contact angle according to the number of thin films of the thin film manufactured in Example 1, and FIG. 3 shows a contact angle according to a 7-OTS injection time.

Referring to FIGS. 2 and 3, it can be seen that the contact angle changes periodically according to each step.

TEM analysis

4 is a cross-sectional TEM photograph of the thin film prepared in Example 1.

Referring to FIG. 4, it can be seen that the self-assembled organic monolayer and the metal hydroxide monolayer are alternately stacked. In this case, it can be seen that the self-assembled organic monolayer has a thickness of 1 nm and the metal hydroxide monolayer has a thickness of 0.1 nm.

5 is a graph showing a change in thickness according to the number of thin films of the thin film manufactured in Example 1. FIG.

Referring to FIG. 5, it can be seen that the thickness of the self-assembled organic monolayer and the metal hydroxide monolayer increased linearly as the number of cycles increased.

Experimental Example 2

In order to determine the electrical leakage characteristics of the thin film obtained in Example 1 and the thin film of Reference Example 1, a leakage current was measured by applying a voltage at -5V to 5V.

6 is a graph showing a change in electrical leakage according to the voltage of the thin film of Example 1, Figure 7 is a graph showing a change in electrical leakage according to the voltage of the thin film of Reference Example 1.

Referring to FIG. 6, in the case of the multilayer molecular film of Example 1, the leakage current decreased as the molecular films were stacked, and in the case of five depositions, 10 ⁻⁶ A / cm ² at 3 V. The following values were shown. In comparison, the results of FIG. 7 show that the value of 10 ⁻⁴ A / cm ² at the same voltage in the case of 90 depositions of Reference Example 1. FIG.

These results indicate that the multilayered molecular film prepared according to the present invention can be better used as an insulating film even when a thin film is formed at a thinner thickness by reducing leakage current even at a thickness of about 5.5 nm (five times deposition). .

1 is an XPS graph of a thin film prepared in Example 1.

2 is a graph showing a contact angle according to the number of thin films of the thin film manufactured in Example 1. FIG.

Figure 3 shows the contact angle according to the 7-OTS injection time when manufacturing a thin film in Example 1.

4 is a cross-sectional TEM photograph of the thin film prepared in Example 1.

5 is a graph showing a change in thickness according to the number of thin films of the thin film manufactured in Example 1. FIG.

6 is a graph showing a change in electrical leakage according to the voltage of the thin film of Example 1.

7 is a graph showing a change in electrical leakage according to the voltage of the thin film of Reference Example 1.

Claims (13)

(S1) forming a self-assembled organic monomolecular film on the surface of the substrate by vapor phase reaction using Molecular Layer Deposition (MLD); (S2) treating the substrate with O ₃ to replace the terminal group of the self-assembled organic monomolecular film with -OH or -COOH; And (S3) forming a metal hydroxide monomolecular layer by reacting a metal precursor on the self-assembled organic monomolecular film by atomic layer deposition (ALD); Method for producing a self-assembled multilayer molecular film is performed by repeating the steps (S1) to (S3) as one cycle. The method of claim 1, The self-assembled organic monolayer a1) after loading the substrate into the chamber, operate the vacuum apparatus to regulate the pressure in the chamber, a2) controlling the temperature in the chamber while flowing purge gas into the chamber, a3) supplying a raw material gas and H ₂ O to form a self-assembled organic monomolecular film into the chamber to form a self-assembled organic monomolecular film on the substrate, a4) A method for producing a self-assembled multilayer molecular film, which is carried out by introducing a purge gas to remove unreacted raw gas, unreacted H ₂ O or deposition by-products. The method of claim 2, The raw material gas includes a fatty acid containing a C1 to C20 alkyl group, an alkyltrihalosilane containing a C1 to C20 alkyl group, an alkyltrialkoxysilane containing a C1 to C20 alkyl group, and an alkyl containing a C1 to C20 alkyl group. A method for producing a self-assembled multilayer molecular membrane, which is one selected from the group consisting of siloxane, alkylthiol containing alkyl groups of C1 to C20, alkylpospaces containing alkyl groups of C1 to C20, and combinations thereof. The method of claim 2, When the molecular layer is deposited, the pressure in the chamber is 300 to 350 mTorr, the chamber temperature is 130 to 150 ° C., the substrate temperature is adjusted to 150 to 250 ° C., and the purging gas is performed by injecting Ar or N ₂ at 20 to 60 sccm. Method for producing a self-assembled multilayer molecular membrane. The method of claim 2, Method of producing a self-assembled multilayer molecular film is carried out so that the ratio of the vapor pressure of the source gas and H ₂ O to 3: 1 to 1: 3 during the molecular layer deposition. The method of claim 2, The vapor pressure of the raw material gas and H ₂ O when the molecular layer deposition is performed to be 40 to 60 mTorr, respectively. The method of claim 1, The O ₃ treatment is performed by injecting for 30 seconds to 1 minute while maintaining the pressure in the chamber at 50 to 100 mTorr. The method of claim 1, The metal hydroxide monolayer is c1) a metal source gas and H ₂ O are introduced in a pulse form and deposited on a substrate; c2) reacting the metal raw material gas with a self-assembled organic monolayer to form a metal hydroxide monolayer, c3) forming a self-assembled multilayer molecular film by introducing a purge gas to remove unreacted raw material gas, unreacted H ₂ O or deposition by-products. The method of claim 8, The metal raw material gas may be alkoxide, chloride, hydroxide, oxyhydroxide, nitrate, carbonate, containing a metal selected from the group consisting of Al, Si, Zr, Ti, Hf, La, Ta, Mg, and combinations thereof. A method for producing a self-assembled multilayer molecular membrane consisting of acetate, oxalate and a mixture thereof. The method of claim 8, The method of manufacturing a self-assembled multilayer molecular film is to perform a ratio of the vapor pressure of the metal source gas and H ₂ O to 3: 1 to 1: 3 when the metal hydroxide monolayer is deposited. The method of claim 8, The vapor deposition of the metal raw material gas and H ₂ O during the deposition of the metal hydroxide monomolecular layer is performed to be 40 to 60 mTorr, respectively. The method of claim 1, Further (S1) is a method for producing a self-assembled multi-layered molecular membrane to be carried out before the (S1). The method of claim 12, The pretreatment removes contaminants on the surface of the substrate by washing the substrate with distilled water and ethanol, and purging with N ₂ gas two or three times. A method for producing a self-assembled multilayer molecular film, which is a step of forming an oxide film on the surface of a substrate by treating the surface of the substrate with O ₃ .

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