KR101213291B1 - Method And System for forming a thin film using an Liquid-Vapor Hybrid Atomic Layer Deposition Method - Google Patents

Abstract

The present invention has been a significant improvement on the atomic layer thin film formation method (ALD).
According to the present invention, a physical adsorbent except that the reactant is prepared as a liquid under normal pressure without a vacuum chamber, the substrate is immersed in and removed from the reactant solution, and then purged to chemically react on the surface of the substrate to form a primary thin film. The (ligand) may be removed, and a reactant having a greater chemical bonding force with the primary thin film than the ligand may be prepared as a liquid, soaked and removed from the substrate, and then purged to form a desired thin film having an atomic layer thickness.

Description

Liquid Gas Hybrid Atomic Layer Deposition Method and System for Forming Thin Film Using The Same [Method And System for forming a thin film using an Liquid-Vapor Hybrid Atomic Layer Deposition Method}

The present invention relates to a method for forming a thin film using a surface reaction, and more particularly, it is possible to reduce production costs by not using a vacuum, and a novel atom characterized in that a raw material liquid and a reaction liquid are sequentially supplied separately from each other. A thin film formation method by a layer vapor deposition method.

In general, the thin film is a general insulation, high dielectric dielectric, wiring, electrode used in various fields such as semiconductor devices, liquid-crystal display, electroluminescent thin film display, steel, non-steel It is commonly used to make metal diffusion barrier, anti-corrosion and anti-oxidation film.

The thin film is sol-gel, electro-plating, sputtering, evaporation, chemical vapor deposition and atomic layer deposition. It may be formed by a variety of methods.

The sol-gel method is one of the wet processes and has the advantage of lowering the production cost because no vacuum is used. However, the sol-gel method is generally less dense than the vacuum method, so the electrical characteristics are lower than those of the vacuum method. And it has a disadvantage of low corrosion resistance and oxidation resistance. The electroplating method in the wet process can obtain a dense film compared to the sol-gel method, but when applied to a large-area product has a disadvantage that it is very difficult to obtain a uniform thickness due to the phenomenon that the current is concentrated at a specific point.

In sputtering, vapor deposition, and chemical vapor deposition, production costs are greatly increased due to the use of a vacuum process. However, the sputtering, vapor deposition, and chemical vapor deposition methods are widely used because they have the advantage of obtaining a dense and uniform film as compared with a general wet method. However, in the case of the sputtering method, since the step coverage of the formed thin film is poor, it cannot be used to form a film of uniform thickness on the uneven surface. Chemical vapor deposition has been widely applied because of better step coverage than sputtering, less damage to the substrate on which the thin film is deposited, lower deposition cost of the thin film, and mass production of the thin film. In sub-micron structures, there is a limit to obtaining uniform thickness or obtaining excellent step coverage. In addition, however, in general chemical vapor deposition, it is difficult to form a film having a desired composition and properties because it simultaneously supplies the raw materials required for film formation. Getting very difficult. In addition, when various reaction raw materials used for forming a thin film react severely in a gaseous state, many impurities remain in the thin film, which may cause deterioration of thin film properties.

Therefore, unlike chemical vapor deposition which simultaneously injects all the conventional process gases, two or more reaction gases necessary to obtain a desired thin film are sequentially divided and supplied according to time so as not to meet in the gas phase, and the supply cycle is repeated periodically to repeat the thin film. The atomic layer deposition method to be formed has been widely used to date since it was presented in US Patent Nos. 4,058,430 and 4,398,973 in 1977 by Suntola et al. Compared with chemical vapor deposition, the ALD method has the advantage of obtaining superior step coverage and a low temperature process, and is capable of manufacturing a thin film with a precise thickness and composition controlled over a large area. The ALD method is widely used in the fields of semiconductor devices, liquid crystal display devices, electroluminescent thin film display devices, etc. which require uniform thin film formation in a large area, and is widely used due to the advantage of being easily applicable to nano-size structures. In the process.

For example, ALD is widely used to form oxides, nitrides, and metal thin films of several to several tens of nanometers in 3D holes or trench structures in semiconductor manufacturing. In addition, recently, ALD is used to form a desired thin film on a nano-template that is easy to make and inexpensive to manufacture, and thus, various nano materials such as nanotubes, nano thin films, nano particles, and nanowires composed of various materials. It is used as a method for manufacturing them. Compared to directly manufacturing various nanomaterials such as nanotubes, nano thin films, nanoparticles, and nanowires by required materials, nanotubes, nano thin films, nanoparticles are deposited by atomic layer deposition on nanoframes, which are easy to make and inexpensive to manufacture. It is easy to manufacture a variety of nano materials, such as nanowires, and has the advantage of producing nanomaterials of various materials. In recent years, atomic layer deposition has also been used to produce steel and non-steel materials having excellent corrosion resistance, oxidation resistance, and appearance characteristics. In other words, by depositing a thin film using the atomic layer deposition method on the surface of the steel and non-steel material to form a thin film in accordance with the shape of the pores (pores) or surface defects of the steel and non-steel material, excellent corrosion resistance and oxidation resistance, Appearance characteristics can be imparted.

However, the above-described atomic layer deposition method has been pointed out that the production cost is high by using the vacuum method, the manufacturing cost is large because the consumption of the precursor is large, and the low deposition rate is disadvantageous. Therefore, in order to manufacture a product in the actual industry, the development of a new method that can solve the above problems while taking advantage of the large area thickness uniformity, precise thickness control characteristics, and step coverage of the conventional vacuum atomic layer deposition method. This is necessary.

Until recently, efforts have been made to solve the above drawbacks of atomic layer deposition. That is, the plasma is generated by synchronizing the supply cycle of supplying the reaction gas, flushing out the remaining reaction gas in the reactor with the purge gas, supplying another reaction gas, and flushing the reactor with the purge gas. The method of forming is presented in Korean Patent Application No. 99-11877 and PCT application PCT / KR00 / 00310 based on the same, and the film growth rate per unit time can be shortened because the supply cycle of the reaction gas can be shortened compared to the conventional method. Can increase. On the other hand, batch type atomic layer deposition method for increasing the productivity of atomic layer deposition method by exposing to the chambers for reaction gas 1, purge gas, reaction gas 2, purge gas which are sequentially fixed by rotating several substrates This is disclosed in Korean Patent Application No. 10-2004-0008629. However, the above-mentioned methods have a limitation in reducing the production cost due to the limitation of using the vacuum method, and cannot solve the disadvantage of the large consumption of the precursor.

Therefore, the main object of the present invention is to provide a method for manufacturing a thin film by reducing the production cost by solving the fundamental disadvantage of the conventional vacuum atomic layer deposition method described above.

That is, the present invention provides a vacuum atomic layer that is easy to control existing thickness and composition, has excellent thickness uniformity of a thin film formed on a large area substrate, and has excellent step coverage for 3D nanostructures. Since the vacuum is not used while maintaining the advantages of the vapor deposition method, a novel thin film manufacturing method having a reduced production cost is provided.

The first object of the present invention is to easily control the thickness and composition, to excellent thickness uniformity of a thin film formed on a large-area substrate, and to have excellent step coverage characteristics for 3D nanostructures. It is to provide a novel atomic layer deposition method that can reduce the cost of thin film production without using a vacuum while maintaining the advantages of the layer deposition method.

The second object of the present invention is to provide a method for reducing additional production costs by providing a method for reducing unnecessary consumption and recycling of a reaction liquid in forming a thin film through the novel atomic layer deposition method. have.

Still other objects of the present invention will become more apparent through the embodiments of the present invention described below.

The present invention includes a step (A) of immersing a substrate in a liquid container containing a first reactant comprising an element and a ligand forming a thin film in a liquid state (A);
A first purge step (B) of removing the substrate from the first reactant and purging with a purge gas to remove the physically adsorbed first reactant;
The second reactant, which is capable of chemically reacting with the ligand of the first reactant to form a substance, is immersed in a liquid container containing a second reactant which is capable of chemically adsorbing the first reactant. (C) forming a material layer in atomic layer units by chemical reaction of the second reactant; And
A second purge step (D) of purging the substrate with a purge gas to remove the by-products generated by the chemical reaction of the chemically adsorbed first reactant and the second reactant and the second reactant adsorbed excessively;
The purge gas may provide a liquid gas hybrid atomic layer deposition method, wherein the purge gas is configured not to react with the first reactant and the second reactant.
In addition, the present invention is a liquid gas hybrid atomic layer deposition method characterized in that all of the above steps (A) to (D) are integrated into one cycle, and the cycle is repeated a plurality of times to deposit a material layer having a desired thickness. It is possible to provide a thin film forming method using.
In addition, the present invention,
A first container containing a first reactant including an element and a ligand forming a thin film in a liquid state;
A first purge device for purging the substrate submerged in the first container with purge gas;
A second container containing a second reactant to immerse the substrate in a second reactant after the purge in the first purge device; and
And a second purge device for purging the substrate submerged in the second container with a purge gas.
The purge gas is configured not to react with the first reactant and the second reactant,
The first container, the first purge device, the second container and the second purge device are sequentially arranged in a circle or in a row,
The first reactant filled in the first container includes an element and a ligand forming a thin film to adsorb the first reactant on a substrate.
The first purge device purges the substrate with a purge gas to remove the physically adsorbed first reactant, leaving only the chemically adsorbed first reactant,
The second reactant filled in the second container forms a material layer in atomic layer units through a chemical reaction with a ligand of the first reactant chemically adsorbed to the substrate,
The second purge device purges the substrate with a purge gas to remove the by-products generated by the chemical reaction between the first reactant and the second reactant and the second physically adsorbed second reactant. A thin film forming system using a liquid gas hybrid atomic layer deposition method can be provided.
In addition, the present invention is an in-line liquid gas in which a predetermined thin film is formed by repeatedly arranging a plurality of deposition groups using the thin film forming system using the liquid gas hybrid atomic layer deposition method as one deposition group. A thin film formation system using a hybrid atomic layer deposition method can be provided.
In addition, the present invention,
A first container containing a first reactant including an element and a ligand forming a thin film in a liquid state;
A purge device for purging the substrate with the purge gas; And
A second container containing a second reactant;
The purge gas is configured not to react with the first reactant and the second reactant,
The substrate is immersed in the first container and taken out by the substrate transfer means to be first purged in the purge device, and then the substrate is immersed in the second container and taken out in the second purge device,
The first reactant contained in the first container includes an element and a ligand forming a thin film to adsorb the first reactant on a substrate.
The purge device purges the substrate with a purge gas in the primary purge to remove the physically adsorbed first reactant, leaving only the chemically adsorbed first reactant,
The second reactant contained in the second container may form a material layer in atomic layer units through a chemical reaction with a ligand of the first reactant chemically adsorbed on the substrate,
The purge device purges the substrate with a purge gas in a secondary purge to remove surface reactions that remove by-products generated by a chemical reaction between the first reactant and the second reactant and an excessively physically adsorbed second reactant. It is possible to provide a thin film formation system using a liquid gas hybrid atomic layer deposition method.
In addition, in the atomic layer deposition method, the time that the substrate is immersed in the first reactant and the time the substrate is immersed in the second reactant is 0.1 sec to 60 sec, the temperature of the first reactant and the second The temperature of the reactants is between 20 ° C. and below the pyrolysis temperature of the first reactants,
In the first purge step and the second purge step, the purge time by the purge gas is 0.1 sec / m ² to 10 min / m ² , the pressure of the purge gas is characterized in that the liquid gas of 0.1 Torr to 7600 Torr A hybrid atomic layer deposition method can be provided.
In addition, in the thin film forming system, the time that the substrate is immersed in the first vessel containing the first reactant and the time the substrate is immersed in the second vessel containing the second reactant is 0.1 sec to 60 sec Wherein the temperature of the first reactant and the second reactant is between 20 ° C. and below the pyrolysis temperature of the first reactant,
The purge by the purge gas injected into the first purge device and the purge gas injected into the second purge device has a purge time per unit area of 0.1 sec / m ² to 10 min / m ^2, and the pressure of the purge gas is 0.1 Torr. It is possible to provide a thin film forming system using a liquid gas hybrid atomic layer deposition method, characterized in that from to 7600 Torr.
In addition, in the atomic layer deposition method, the first purge step and the second purge step, respectively, by adjusting the purge time or the pressure of the purge gas, the first purge step and the second purge step, respectively The liquid gas hybrid atomic layer deposition method may include removing a part of the first reactant physically adsorbed and a second reactant excessively adsorbed by the by-product and leaving a part of the second reactant.
In the thin film forming system, the first reactant physically adsorbed by mutually adjusting the pressure and purge time of the purge gas injected into the first purge device and the second purge device; A thin film forming system using a liquid gas hybrid atomic layer deposition method may be used to remove only part of the by-product and the second reactant adsorbed physically and part of the second reactant.
In addition, the present invention provides a thin film forming system using the liquid gas hybrid atomic layer deposition method described above (same as claim 5) as one deposition group, and repeatedly depositing a plurality of deposition groups to form a predetermined thin film. It is possible to provide a thin film formation system using a liquid gas hybrid atomic layer deposition method of the line) method.
In addition, the present invention, by controlling the pressure and the purge time of the purge gas injected into the purge device, by removing only a part of the physically adsorbed first reactant and the by-product and the physically adsorbed second reactant It is possible to provide a thin film formation system using a liquid gas hybrid atomic layer deposition method, in which some remain.
In addition, the present invention, the time that the substrate is immersed in the first vessel containing the first reactant and the time the substrate is immersed in the second vessel containing the second reactant is 0.1 sec to 60 sec, the first reactant and the first 2 the temperature of the reactant is 20 ° C. to below the thermal decomposition temperature of the first reactant,
Purging by the purge gas injected into the purge device, the purge time per unit area is 0.1 sec / m ² to 10 min / m ² , the liquid gas hybrid atomic layer characterized in that the pressure of the purge gas is 0.1 Torr to 7600 Torr A thin film forming system using a vapor deposition method can be provided.

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As described above, accurate thin film thickness and composition control of sub-nano size is easy, excellent layer covering properties for ultra-fine 3D structures, and excellent thickness uniformity for large-area substrates, but also relatively high production cost. It is possible to produce a thin film having a low and high thin film deposition rate.

In addition, even in the case where it is difficult to use a vacuum chamber such as stainless steel having a large area, a coating for providing functionality can be provided with an inline system, which can provide a high functional improvement while dramatically reducing the cost and effort of the surface treatment process. Can be.

1 is a flowchart illustrating a thin film formation process of the liquid gas hybrid atomic layer deposition method of the present invention.
FIG. 2 is a schematic view for explaining the atomic layer thin film forming apparatus used in the thin film forming method using the liquid gas hybrid atomic layer deposition method of the present invention.
3A to 3B are views illustrating a specific atomic layer thin film forming apparatus used in the thin film forming method using the liquid gas hybrid atomic layer deposition method according to an embodiment of the present invention.
FIG. 4 is a diagram illustrating an increase in thickness depending on the number of repetitions of a TiO ₂ thin film deposited using a liquid gas hybrid atomic layer deposition method according to an embodiment of the present invention.
FIG. 5 is a diagram showing an X-ray diffraction analysis of a TiO ₂ thin film deposited using a liquid gas hybrid atomic layer deposition method according to an embodiment of the present invention.
6a to 6b are views showing the configuration of a liquid gas hybrid atomic layer thin film formation system that can reduce the production time and cost.

Hereinafter, with reference to the accompanying drawings will be described an embodiment of the present invention; However, embodiments of the present invention illustrated below may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

1 is a schematic view for explaining a liquid-Vapor Hybrid Atomic Layer Deposition of the present invention.

In order to achieve the above technical problem, the method for forming a thin film using the novel atomic layer deposition method according to the present invention impregnates a substrate in a liquid container containing a first reactant including an element and a ligand constituting a thin film in a first state on a substrate. Adsorb the reaction. At this time, since the chemical adsorption and the physical adsorption of the first reactant occur simultaneously on the surface of the substrate, it is necessary to remove the physically adsorbed first reactant (eg, the first reactant having a van der Waals bond). Thus, the substrate is removed from the first reactant and then purged with an inert gas (first purge) to remove the physically adsorbed first reactant from the first reactant, leaving only the first adsorbed chemically on the surface. Subsequently, the first chemically adsorbed substrate is immersed in a liquid container containing a second reactant capable of chemically reacting the substrate on which the first chemically adsorbed reactant remains with the ligand of the first reactant to form a substance. The chemical reaction of the reactant and the second reactant forms a material layer in atomic layer units. Then, the by-products produced by the chemical reaction between the first and second reactants and the second adsorbates excessively adsorbed are purged with an inert gas (second purge). The desired compound thin film can thus be obtained at the level of atomic layer thickness. So-called liquid gas hybrid atomic layer chemical vapor deposition (Atomic Layer Chemical Vapor Deposition) is a thin film formation. As is widely known, the purge may be performed by supplying a sufficient amount of purge gas while the discharge port of the chamber is opened, and there are no particular limitations on the substrate transfer means for submerging the substrate into the reactant and transporting it to the chamber for purging. , Rollers, conveyors, as well as people can be transported directly. The chucking of the substrate may also be any arbitrary chuck such as a well-known vacuum chuck, a magnetic chuck, a mechanical jig or a chuck using a holder.

In addition, each step may be repeated in cycles to obtain the desired thickness.

In addition, by adjusting the purge time in the first and second purge, it is also possible to form a layer of material of a desired thickness by partially remaining without completely removing the physically bound reactants. Such a method requires high productivity and is particularly advantageous when applied to the steel industry using a large area plate as a substrate.

In the above, the reactant liquid may be used by using the raw material liquid stock solution, or by dissolving the raw material liquid in a solvent. At this time, the concentration of the raw material liquid is adjusted to 1 to 100% depending on the viscosity of the liquid (whether or not the material is well purged) and may vary depending on the type of chemical to be deposited. The temperature of the reactant liquid may vary depending on the reactivity of each component, but the maximum limit temperature should be kept below the temperature at which the molecules forming the starting liquid are pyrolyzed.

FIG. 2 is a schematic view for explaining the atomic layer thin film forming apparatus used in the thin film forming method using the liquid gas hybrid atomic layer deposition method of the present invention. Specifically, the gas-liquid hybrid atomic layer thin film forming apparatus used in the method for forming an atomic layer thin film of the present invention comprises a container containing a raw material liquid as a first reactant, and a nozzle capable of blowing an inert gas having little or no reactivity such as N _2. And a container containing the reaction liquid as the second reactant, and a substrate.

The purge gas may be an inert gas that does not react with the first reactant (raw liquid) and the second reactant (react liquid), for example, N ₂ , Ar, Xe, air (not containing water), and the like. And the purge time and pressure depend on the nozzle and device design, the purge time and pressure range can be configured in various states with mutual control.

Hereinafter, an embodiment of a thin film forming method using the atomic layer thin film forming apparatus of FIG. 2 will be described with reference to FIGS. 3 to 5.

<Examples>

3A and 3B are views illustrating a specific atomic layer thin film forming system used in a thin film forming method using a liquid gas hybrid atomic layer deposition method according to an embodiment of the present invention. As shown in FIG. 3A, (1) the first vessel containing the first reactant, (2) the first purge apparatus, (3) the second vessel containing the second reactant, and (4) the second purge apparatus are arranged in a circular shape. , Sequentially rotating, or as shown in Figure 3b, (1) the first vessel containing the first reactant, (2) the first purge device, (3) the second vessel containing the second reactant and (4) The second purge devices may be arranged in a line and configured to be sequentially arranged.

Specifically, the silicon substrate is immersed in a container containing TTIP (Ti {OCH (CH ₃ ) ₂ } ₄ ) solution, which is a first reactant composed of a thin film element and ligand, and then chemically adsorbs the first reactant onto the substrate. 1 The first reactant, which is physically bound in the purge section by the purge device, is removed by purging the inert gas. Here TTIP is generally 5 ~ 10%, the solvent can be prepared by using toluene (benzene), benzene (benzene). Preparation of the solution and the following immersion treatment can be carried out at a temperature above room temperature, 250 ° C or less of pyrolysis temperature of TTIP, in the present embodiment was carried out at room temperature. At this time, the time to immerse in the TTIP solution to chemisorb the first reactant on the substrate is 0.1 sec ~ 20 sec. In addition, in order to purge the first reactant that is physically bonded with an inert gas, the pressure of the inert gas is 0.1 Torr to 7600 Torr, and the purge time is applied for 0.1 sec / m ² to 10 min / m ² . If the pressure of the inert gas is high, the purge time can be reduced, and if it is low, the purge time should be relatively long.

Subsequently, when the substrate is immersed in a vessel containing DI-water, which is the second reactant, the second reactant causes a hydrolysis reaction with the ligand of the first reactant chemisorbed on the substrate. A TiO ₂ film in atomic layer units is formed.

Formula 1

Ti {OCH (CH ₃ ) ₂ } ₄ + 2H ₂ O → TiO ₂ +4 (CH ₃ ) ₂ CHOH

In addition to the pure water in the process may be used to dilute pure water in ethanol (ethanol). At this time, ethanol is highly volatile to facilitate purge. At this time, the time for immersing the second reactant on the substrate is 0.1 sec to 20 sec for pure water, and 0.1 sec to 40 sec for pure water diluted with ethanol.

Next, in the purge section by the second purge apparatus, 4 (CH ₃ ) ₂ CHOH as a by-product and the second reactant adsorbed excessively are purged with an inert gas. The pressure of the inert gas is 0.1 Torr ~ 7600 Torr, and the purge time is between 0.1 sec / m ² ~ 10 min / m ² . If the pressure of the inert gas is high, the purge time can be reduced, and if it is low, the purge time should be relatively long. Subsequently, it is confirmed whether the thickness of the formed TiO ₂ film is an appropriate thickness, and each step is repeated in cycles as necessary.

Figure 4 shows the change of the thickness according to the cycle of the TiO ₂ material layer deposited using the liquid gas hybrid atomic layer deposition method of the present invention. A solution obtained by diluting TTIP as the first reactant and pure water in ethanol as the second reactant was used, and N ₂ gas was used as the first purge and the second purge gas. As can be seen in Figure 3, it can be seen that it is possible to easily form a TiO ₂ layer having a desired thickness by repeating the cycle as many times as you like, because the TiO ₂ layer of a predetermined thickness (1.8Å / cycle) formed through one cycle .

5 shows X-ray diffractometer (XRD) results of the TiO ₂ thin film according to an embodiment of the present invention. As can be seen from the X-ray diffraction analysis, it can be seen that a TiO ₂ thin film having a rutile phase was formed.

In particular, such a liquid gas hybrid atomic layer thin film forming system is particularly useful for coating to improve appearance and corrosion resistance on large area substrates such as stainless steel. In the case of a large-area substrate, a considerable cost and effort are required to construct a vacuum chamber that is suitable for the large-area substrate. Therefore, the method for forming an atomic layer thin film using the immersion and purge of the present invention is very useful as a coating for imparting various functionalities to a large area stainless steel. In other words, the method of forming a functional coating on the surface of a large-area substrate is a method of forming a liquid gas hybrid atomic layer thin film formation system that can reduce production time and cost, and includes a first reactant containing an element and a ligand forming a thin film. Inline liquid gas hybrid atomic layer thin film formation system comprising a solution bath, a first purge system, a second solution bath containing a second reactant capable of reacting with a material layer formed by reactants of the first solution bath, and a second purge system. It can be configured as an in-line system. At this time, the first solution bath containing the reactants including the elements and ligands forming the thin film, the first purge device, the second solution bath containing the second reactant capable of chemically reacting with the reactants of the chemisorbed first solution bath Since a thin film having a constant thickness is formed while passing through the purge device, in order to form a thin film having a desired thickness, as shown in FIG. 6A, (1) a first container, (2) a first purge device, (3) a second container, and ( 4) The hybrid atomic layer deposition system composed of the second purge device is sequentially arranged in a row by the required number of repetitions (n times) (for example, the first container, the first purge device, the second container, and the second purge device). To provide a thin film forming system using an in-line liquid gas hybrid atomic layer deposition method capable of forming a required thin film thickness. Can be.

In addition, as shown in Fig. 6B, the system is composed of (1) the first container, (2) the purge device, and (3) the second container using the first purge device and the second purge device using one purge device, By constructing one cycle of going through 1) the first vessel, (2) the purge device, (3) the second vessel, and (2) the purge device, production time can be reduced by minimizing the time taken to repeat one cycle. have. In this case, the cost of constructing the purge device can also be reduced by half.

In addition, although the TiO ₂ coating is mentioned in the above embodiment, the coating material is not limited thereto, and may be very diverse, such as ZrO ₂ , SiO ₂ , and Al ₂ O ₃ .

Claims (12)

(A) immersing a substrate in a liquid container containing a first reactant comprising an element and a ligand forming a thin film in a liquid state (A);
A first purge step (B) of removing the substrate from the first reactant and purging with a purge gas to remove the physically adsorbed first reactant;
The second reactant, which is capable of chemically reacting with the ligand of the first reactant to form a substance, is immersed in a liquid container containing a second reactant which is capable of chemically adsorbing the first reactant. (C) forming a material layer in atomic layer units by chemical reaction of the second reactant; And
A second purge step (D) of purging the substrate with a purge gas to remove the by-products generated by the chemical reaction of the chemically adsorbed first reactant and the second reactant and the second reactant adsorbed excessively;
And the purge gas is configured to not react with the first reactant and the second reactant. A method of forming a thin film using a liquid-gas hybrid atomic layer deposition method comprising combining all of the steps (A) to (D) of claim 1 to form one cycle, and repeating the cycle a plurality of times to stack a material layer having a desired thickness. . A first container containing a first reactant including an element and a ligand forming a thin film in a liquid state;
A first purge device for purging the substrate submerged in the first container with purge gas;
A second container containing a second reactant to immerse the substrate in a second reactant after the purge in the first purge device; and
And a second purge device for purging the substrate submerged in the second container with a purge gas.
The purge gas is configured not to react with the first reactant and the second reactant,
The first container, the first purge device, the second container and the second purge device are sequentially arranged in a circle or in a row,
The first reactant filled in the first container includes an element and a ligand forming a thin film to adsorb the first reactant on a substrate.
The first purge device purges the substrate with a purge gas to remove the physically adsorbed first reactant, leaving only the chemically adsorbed first reactant,
The second reactant filled in the second container forms a material layer in atomic layer units through a chemical reaction with a ligand of the first reactant chemically adsorbed to the substrate,
The second purge device purges the substrate with a purge gas to remove the by-products generated by the chemical reaction between the first reactant and the second reactant and the second physically adsorbed second reactant. Thin film formation system using liquid gas hybrid atomic layer deposition. An in-line liquid gas hybrid atomic layer deposition method in which a thin film forming system using the liquid gas hybrid atomic layer deposition method of claim 3 is formed as a deposition group, and a plurality of deposition groups are repeatedly arranged to form a predetermined thin film. Thin film forming system using. A first container containing a first reactant including an element and a ligand forming a thin film in a liquid state;
A purge device for purging the substrate with the purge gas; And
A second container containing a second reactant;
The purge gas is configured not to react with the first reactant and the second reactant,
The substrate is immersed in the first container and taken out by the substrate transfer means to be first purged in the purge device, and then the substrate is immersed in the second container and taken out in the second purge device,
The first reactant contained in the first container includes an element and a ligand forming a thin film to adsorb the first reactant on a substrate.
The purge device purges the substrate with a purge gas in the primary purge to remove the physically adsorbed first reactant, leaving only the chemically adsorbed first reactant,
The second reactant contained in the second container may form a material layer in atomic layer units through a chemical reaction with a ligand of the first reactant chemically adsorbed on the substrate,
The purge device purges the substrate with a purge gas in a secondary purge to remove surface reactions that remove by-products generated by a chemical reaction between the first reactant and the second reactant and an excessively physically adsorbed second reactant. Thin film formation system using liquid gas hybrid atomic layer deposition. The method of claim 1, wherein the substrate is immersed in the first reactant and the substrate is immersed in the second reactant is 0.1 sec to 60 sec, the temperature of the first reactant and the temperature of the second reactant is 20 ℃ to Below the pyrolysis temperature of the first reactant,
In the first purge step and the second purge step, the purge time by the purge gas is 0.1 sec / m ² to 10 min / m ² , the pressure of the purge gas is characterized in that the liquid gas of 0.1 Torr to 7600 Torr Hybrid atomic layer deposition. The method of claim 3, wherein the substrate is immersed in the first vessel containing the first reactant and the substrate is immersed in the second vessel containing the second reactant is 0.1 sec to 60 sec. 2 the temperature of the reactant is 20 ° C. to below the thermal decomposition temperature of the first reactant,
The purge by the purge gas injected into the first purge device and the purge gas injected into the second purge device has a purge time per unit area of 0.1 sec / m ² to 10 min / m ^2, and the pressure of the purge gas is 0.1 Torr. Thin film formation system using a liquid gas hybrid atomic layer deposition method, characterized in that from 7600 Torr. The method of claim 1, wherein the first purge step and the second purge step, respectively, by adjusting the purge time or the pressure of the purge gas, the first purge step and the second purge step, respectively, the physically adsorbed agent The liquid gas hybrid atomic layer deposition method of claim 1, wherein only a part of the reactants and the second reactant adsorbed excessively by the by-products are removed and some remain. 4. The physically adsorbed first reactant and the byproduct and the physical adsorption of claim 3, wherein the pressure and purge time of the purge gas injected into the first purge device and the second purge device are mutually adjusted. A thin film forming system using a liquid gas hybrid atomic layer deposition method, characterized in that only part of the second reactant is removed and part is left. An in-line liquid gas hybrid atomic layer deposition method in which a thin film formation system using the liquid gas hybrid atomic layer deposition method of claim 5 is formed as one deposition group by repeatedly arranging a plurality of deposition groups to form a predetermined thin film. Thin film forming system using.


The method of claim 5, wherein the pressure and purge time of the purge gas injected into the purge device are mutually controlled to remove only a part of the physically adsorbed first reactant and the by-product and the physically adsorbed second reactant. A thin film formation system using liquid gas hybrid atomic layer deposition, characterized in that some remain. The method of claim 5, wherein the substrate is immersed in the first vessel containing the first reactant and the time of the substrate immersed in the second vessel containing the second reactant is 0.1 sec to 60 sec. 2 the temperature of the reactant is 20 ° C. to below the thermal decomposition temperature of the first reactant,
Purging by the purge gas injected into the purge device, the purge time per unit area is 0.1 sec / m ² to 10 min / m ² , the liquid gas hybrid atomic layer characterized in that the pressure of the purge gas is 0.1 Torr to 7600 Torr Thin film formation system using vapor deposition.

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