KR100824328B1 - Ceramic coating method with micro-droplets and partial positive pressure, and coating apparatus therof - Google Patents

Abstract

The present invention relates to a coating method and a device thereof, and to a positive pressure coating method and a device using a local positive pressure and micro droplets. Features of the present invention include the steps of: (a) heating a substrate located at the lower end of the integrated reactor; (b) injecting a precursor of a deposition material component into the reactor through at least one spraying portion in at least a portion of the upper portion of the integrated reactor; And (c) inverting the pressure distribution inside the reactor while the precursor descends to the substrate, thereby depositing an atomized precursor on the substrate.

When the present invention is provided, the solvent and the additives vaporized in the coating reagent-solvent system induce localized high pressure or positive pressure, thereby allowing the precursor complexes to naturally move to the substrate, thereby facilitating thin film production.

In addition, expensive equipment necessary for a ceramic thin film including a transparent conductive film, that is, high vacuum equipment is not required, so that various ceramic thin films can be easily provided and a method that can be continuously processed can reduce the manufacturing cost, thereby enabling mass production.

Positive pressure, reactor, micro drop, coating, ceramic, atomization

Description

FIELD OF THE INVENTION A positive pressure coating method using a local positive pressure and micro droplets and a device therefor {CERAMIC COATING METHOD WITH MICRO-DROPLETS AND PARTIAL POSITIVE PRESSURE, AND COATING APPARATUS THEROF}

1 shows a schematic view of a positive pressure coating apparatus according to the present invention,

2 is a view showing a temperature distribution measured when the substrate temperature is maintained at 500 ° C. for 10 minutes in the reaction chamber of FIG. 1;

Figure 3 is a pressure distribution showing the situation of Figures 1 and 2,

Figure 4 calculates the local pressure change according to the amount introduced when the substrate temperature is heated to 500 degrees in the reaction chamber of FIG. One Graph,

Figure 5 is a view showing the precursor introducer of the micro drop mold used in the positive pressure coating apparatus according to the present invention,

FIG. 6 is a schematic diagram for explaining a strong positive pressure generated locally when the microdroplet precursor is introduced into the upper end of the reactor 10 using the apparatus of FIG. 5;

7 is a schematic diagram comprehensively expressing the principle of the positive pressure coating device according to the present invention,

8 is a schematic view showing that the auxiliary injection unit installed in the reaction tank inner side portion of the positive pressure coating apparatus according to the present invention can be easily turned to the substrate portion or the chamber upper end portion,

9 is a schematic view showing a positive pressure coating device separated into a first chamber for generating a positive pressure and a second chamber for depositing a substrate, as another embodiment according to the present invention;

10 is a view showing a schematic diagram of a positive pressure coating device in which an exhaust pipe is installed in a portion of a lower part of a reactor as another embodiment according to the present invention;

11 and 12 are views showing a positive pressure coating apparatus that can continuously perform a coating process as still another embodiment of the present invention.

FIG. 13 is an SEM image of the resulting WO ₃ thin film when W (CO) ₆ is mixed with cyclohexane reagent at 30% (solubility about 10%) and discharged into the reactor through a micro tube using a micro pump,

FIG. 14 is a solution using SnCl ₄ 5H ₂ O and ethylene glycol (ethylene glycol) using the apparatus of FIG. 9, and coated with precursor microdroplets mixed with ethanol and distilled water 2: 1 as a solvent. SEM photo of thin film,

15 is a solution using SnCl ₄ 5H ₂ O, NH ₄ F, ethylene glycol (ethylene glycol) using the apparatus of Figure 10, the solvent was coated with a precursor microdroplets mixed with ethanol and distilled water Thin film SEM photos,

FIG. 16 is a SEM photograph showing thin film growth behavior according to the amount of precursor introduced into the reactor using the apparatus of FIG. 1 and using the solution of Example 3. FIG.

17 is a SEM photograph of a TiO2 thin film coated using a positive pressure coating apparatus according to the present invention.

The present invention relates to a coating method and an apparatus thereof, and more particularly, to generate a flow onto a substrate using a locally generated strong positive pressure, in which the precursor complex naturally moves over the substrate to obtain various ceramic coatings. Positive pressure coating method and apparatus therefor.

Ceramic coating techniques are conventionally developed in various techniques such as sol-gel, CVD, PVD, plasma spray, thermal spray. Thin film production by the sol-gel method is very cheap and simple, but tends to be of poor quality. On the other hand, the CVD method, the sputtering method, the PLD method and the like have excellent film quality but have a disadvantage in coating a large area because a vacuum equipment must be used.

CVD is a method of vaporizing a precursor under vacuum and low pressure and depositing it on a heated substrate by thermal chemical reaction. The PVD method is a method of obtaining a thin film by depositing cluster-like materials on a substrate through condensation of atomic molecules and plasma condensation generated by applying energy to a target, such as sputtering and laser evaporation. Traditionally, both CVD and PVD methods require high vacuum equipment and thin film manufacturing using low pressure.

Plasma spraying and thermal spraying are a method of eluting a solid material feeder as the primary material and eluting the substrate with plasma or high temperature. All of these require high strength substrates and are widely used in certain industries due to the specificity of the coating.

Of course, in the PVD method, the buffer and the reaction gases are put at an atmospheric pressure or higher to actively use the buffer gas effect and reactive deposition. This is used as a means for controlling the physical properties of the thin film. That is, atoms, molecules, clusters, or generated plasma that are physically separated from PVD are sensitive to the environment. In other words, the cooling effect, mobility, reactivity, etc. is because the physical properties of the product depends on the surrounding gas.

Long ago, a cloud chamber was developed. This has been developed by cluster scholars and used in various fields, which are typically used to manufacture nanoparticles and clusters. The configuration shows that the metal powder is placed in the fog chamber and the entire fog chamber is kept above the melting point of the metal.

The metal then boils and has a significant vapor pressure (tortor) which is present as a uniform mist in the mist chamber. At this time, when the nanoparticles are sent through the pinhole of the mist chamber onto the cooled substrate in a high vacuum, a uniform mist flow is generated and metal nanoparticles are generated on the substrate.

If you expand the mist flow into the carrier gas and perform mass spectrometry, you get a beautiful mass spectrometry pattern from the cluster to the nanoparticles. The basic principle of these fog flows is the pressure difference and selective deposition on the substrate is caused by local temperature differences. However, this method has a problem in that it is limited to a metal having a low melting point.

The object of the present invention is to realize the principle of this fog chamber in a positive pressure atmosphere larger than atmospheric pressure, so that the vacuum equipment is unnecessary. In addition, it is possible to obtain various and high-quality ceramic thin films by CVD, PVD method, which use expensive vacuum equipment, plasma spray, and thermal spray method that use high energy deposition principle. It is to provide a coating method and an apparatus thereof.

In order to achieve the above technical problem, the first feature of the present invention (a) heating the substrate located in the lower end of the integrated reactor; (b) injecting a precursor of a deposition material component into the reactor through at least one spraying portion in at least a portion of the upper portion of the integrated reactor; And (c) inverting the pressure distribution inside the reactor as the precursor descends to the substrate, thereby depositing an atomized precursor (described in detail in the detailed description of mixed gas, liquid, and solid phase) on the substrate. .

And a second feature according to the present invention comprises the steps of: (a) heating a substrate located at the bottom of the second chamber of the integrated reactor in which the first chamber and the second chamber are divided up and down; (b) injecting a precursor of a deposition material component into the first chamber in a predetermined amount through at least one spraying portion in at least a portion of the first chamber; (c) discharging the precursor inside the first chamber into the second chamber through opening of at least one shutter disposed between the first chamber and the second chamber; And (c) depositing the discharged precursor on the substrate.

Here, it is preferable to include an exhaust pipe in at least a portion of the reaction vessel located below the substrate to control the locally generated positive pressure and the concentration of the precursor, wherein the precursor is at least one of a liquid reagent-solvent and a solid reagent-solvent. It is also preferable to use as one.

In addition, the solvent preferably contains at least one or more kinds of organic compound additives having a break point of at least 50 ° C. or higher, and the pressure formed on the substrate by reaction of the precursor is at least 50 Torr or more than the pressure of the substrate portion. Also preferred.

In addition, preferably, the deposition material component may be an organometallic compound including at least one or more chlorine (Cl) ligands, and the deposition material component may include at least one carbon monooxide ligand. It may be made of an organometallic compound, it is also possible to use a ceramic tube having an internal diameter of at least 1μm through the injection portion of the precursor into the reactor.

In addition, it is preferable to connect a gas pipe to the injection unit to introduce the precursor into the reactor at the same time as the gas, and it is also preferable to make the precursor into a sol or gel solution.

According to a third aspect of the present invention, there is provided a reactor including a precursor of a deposition material component to generate a positive pressure; A substrate positioner positioned at a lower end of the reactor; At least one spraying unit discharging the precursor into an upper portion of the reactor to enable deposition on the substrate; And a flow rate controller configured to adjust any one of a flow rate of the precursor introduced into the reactor and a pressure inside the reactor on the side of the reactor.

In addition, a fourth feature according to the present invention comprises: a first chamber positioned above the integrated reaction vessel to react with a precursor of the deposition material component to generate a positive pressure; A second chamber disposed under the reactor to deposit a substrate; An injection unit for discharging the precursor into the first chamber; It includes a substrate position portion for positioning the substrate on the lower end of the second chamber, the first chamber and the second chamber is connected to at least one shutter.

Here, the substrate position portion may include a heater for heating the substrate and a driving device to enable the vertical movement of the substrate, the substrate preheater for preheating the substrate on the outer side of the lower end of the reactor and the coated substrate After the processing further includes a post-processing unit, it is also preferred that the substrate preheating unit, the substrate position portion and the post-processing portion is connected to a conveyor belt to enable the continuous movement of the substrate.

In addition, preferably, the injection unit may be made of a ceramic tube having an internal diameter of at least 1 μm or more, and may further be connected to a gas tube capable of injecting gas into the injection unit, and located at an upper side of the reactor and rotation is performed. It is installed to enable, and may further include an auxiliary injection unit for introducing the precursor into the reactor.

In addition, it is also desirable to include an exhaust pipe in at least a portion of the reaction vessel located below the substrate to control the positive pressure and the concentration of the precursor that occur locally.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a view showing a schematic diagram of a positive pressure coating device according to the present invention.

As shown in FIG. 1, the positive pressure coating device according to the present invention includes a reaction tank, a substrate position part, an adverb part, and a flow rate control part. The substrate 25 is raised in the substrate position portion 20 at the bottom of the reactor 10 and the substrate is uniformly heated by the heater 23 at the bottom of the substrate 10. The height of the substrate can be adjusted by the driving device 27 placed at the bottom. .

The upper end of the reaction tank 10 is installed (for large area coating) multiple injection unit 50, which is a precursor introduction portion, and the secondary injection unit 60 is also installed on the side. On the side of the upper end of the reactor 10, a flow rate adjusting unit 70 which is responsible for gas introduction and precursor discharge is provided. Normally, the amount of precursor and pressure at the top of the precursor are controlled through a pump, and flow control is performed through a flow controller (not shown).

The injection unit 50 and the auxiliary injection unit 60 located at the upper end and the side of the reactor 10 are configured to allow the carrier or the reaction gas to be introduced simultaneously with the precursor. The reactor 10 is made of heat-resistant plastic and has a diameter of about 150 mm and a height of about 400 mm. The reactor 10 may be a ceramic or metal material without corrosion.

If the substrate 25 is heated to about 500 degrees and maintained for 10 minutes before the precursor is introduced, the inside of the reaction tank 10 is in an equilibrium state having a temperature gradient. The temperature near the substrate is the highest and the upper end of the reactor 10 is the lowest.

2 is a view showing a temperature distribution measured when the substrate temperature is maintained at 500 ° C. for 10 minutes in the reaction chamber of FIG. 1. As shown in Figure 2, 5 cm away from the substrate is about 260 ℃, chamber top is 80-90 ℃. At this time, the air in the chamber of the reaction tank 10 has a natural flow toward the upper chamber as shown in FIG. In other words, the air pressure around the substrate 25 has the highest air pressure, and the air in the vicinity generates a strong upper air flow that flows toward the lower temperature, that is, moves to the upper end of the reactor 10. The air flow up to the upper end hits the upper end inside the reactor 10 and flows down again. The temperature of the wall surface is the lowest, so that a downward airflow occurs along the reactor wall and goes out through the bottom of the reactor.

The rising air in the center is a very strong air, and if you put a piece of tissue here, it will blow up to the upper part at once. In this atmosphere, the precursor cannot reach the substrate. Therefore, no deposition is performed on the substrate 25. The reason why these problems have not been studied so far is that in the CVD and PVD method, since the high vacuum and very low environment are used, the rising air over the substrate can be ignored, and the spraying method in which the coating occurs under atmospheric pressure is as strong as the PVD method. This is because kinetic energy (eg, plasma) can reach the substrate through a resistive barrier around it.

3 is a pressure distribution of the situation of FIGS. 1 and 2; It is quite difficult to measure the local pressure of the gas flow at high temperatures. Therefore, the ideal gas equation was used to find the pressure distribution in the reaction chamber. The ideal gas equation is represented by the following equation.

[Equation 1] PV = nRT

P: pressure, V: volume, n: mole number, R: gas constant, T: temperature

Assuming that the reactor 10 is completely sealed, assuming that each temperature region is separated, a pressure distribution occurs as shown in FIG. The actual pressure has a lower value than the pressure distribution of FIG. 3 since the lower end of the reactor 10 has a structure of about 10% open. Therefore, the actual pressure distribution is estimated to be about 30 to 70% of the graph of FIG. 3 from various experimental results and evaluations.

Figure 4 calculates the local pressure change according to the amount introduced when the substrate temperature is heated to 500 degrees in the reaction chamber of FIG. One graph. The calculated value shown in the graph of FIG. 4 used the formula [Equation 1]. It was assumed that the introduced liquids were present at a height of 5-15 cm at the top of the reactor 10 for a very short time. At this time, the temperature is about 130 degrees (about 400K), and at this temperature, ethanol and water evaporate in an instant and exist in a gaseous state. The local pressure is then proportional to the molar number (amount) of solvent introduced. The results are shown in detail in FIG. Introducing about 0.7 ml of water and about 2.8 ml of ethanol results in a pressure equal to the local pressure of 2.6 atm on the substrate 25 inside the closed reactor 10 as shown in the graph of FIG.

Therefore, in the closed chamber, about 0.7 ml of water and about 2.8 ml of ethanol should be added instantaneously, indicating that the opposite gas flow may be reversed to reverse the upward airflow of FIG. 1. In the experiment of the present invention, since the lower end of the reaction tank 10 is slightly open and suction, suction can be caused even in a much smaller amount than these amounts.

5 is a view showing the precursor introducer in the form of micro droplets used in the positive pressure coating apparatus according to the present invention. It is mounted in multiple numbers as a precursor injection part in the upper end part and the side part part of the reaction tank 10 of FIG. Micrometer size (droplet diameter: 1 micrometer minimum) liquid at the top of the reactor 10 using a micropump (syringe pump) and a fused silica tube (approximately 1 to 50 micrometers outlet diameter). Feed the enemy.

The molten silica tube may fasten the gas introduction tube to the side surface by using fittings. In some cases, the reaction gas and the carrier gas can flow into the reaction tank 10 together with the micro droplets through the gas pipe.

FIG. 6 is a schematic diagram for explaining a strong positive pressure generated locally when the microdroplet precursor is introduced into the upper end of the reactor 10 using the apparatus of FIG. 5. 6 is a schematic diagram of a process that occurs when a highly volatile precursor reagent is dissolved or mixed in a solvent, as shown in Example 1 to be described later.

That is, when tungsten carbonyl (W (CO) ₆ ) is dissolved or dispersed in cyclohexane and introduced into the upper end of the reactor 10, the solvent first evaporates in an instant and the atomization (liquid, gas and solid phases are all It is placed in the included phase), which generates a local positive pressure (higher than atmospheric pressure) and then reaches a point of about 200 ° C., whereby tungsten carbonyl is vaporized to give the maximum positive pressure effect with the opportunity solvent. This positive pressure penetrates the substrate through the high pressure around the substrate. At this time, tungsten carbonyl is reactively deposited on the substrate to form WO ₃ , and the solvent exits through the exhaust pipe at the lower end of the reactor.

6 is a schematic diagram showing a reaction process when an additive having a different degree of vaporization by temperature is added in addition to the deposition raw material reagent and the solvent. As described above, when ethylene glycol is mixed with a molecular weight of 80 and 200, it passes through a multistage temperature range in the order of solvent-> ethylene glycol 80-> ethylene glycol 200-> and vaporizes to increase the positive pressure in multiple stages.

In addition, some of the ethylene glycol is combined with the organometallic reagent, resulting in an unvaporized portion. This will cause vaporization at higher temperatures. When vaporization takes place at higher temperatures, all of the liquid components evaporate and vaporize, destructively dispersing the remaining solid particles. As a result, fine precursors reach the substrate and help to obtain a good quality thin film.

7 is a schematic diagram comprehensively expressing the principle of the positive pressure coating device according to the present invention. When the liquid or solid precursors are dissolved in a solvent or simply mixed, the precursors are placed at a boiling point or more, and the solvent is released from the coating reagent-solvent system to locally induce the upper end of the reactor to a high pressure (positive pressure) and to the upper end of the substrate before the precursor is introduced. It reverses strong rising air to falling air. At this time, the precursor is naturally deposited on the substrate by this flow.

Precursors can be deformed by temperature and ambient gas and can be accompanied by chemical reactions and physical changes when hit on a substrate. 7 illustrates this process well. When the solvent evaporates and a local positive pressure occurs, the precursors stay to some degree on the top of the substrate, like a fine cloud or fog. When the precursors are continuously introduced, the pressure distribution is reversed, that is, the upper portion of the reaction vessel 10 changes to a high pressure state and a lower portion of a low pressure state.

8 is a schematic view showing that the auxiliary injection unit installed in the reaction tank inner side portion of the positive pressure coating device according to the present invention can be easily turned to the substrate portion or the upper end of the chamber. By providing the auxiliary injection unit 60 as described above, the precursor and the pressure can be controlled and the coating uniformity can be improved.

9 is a schematic diagram showing a positive pressure coating device separated into a first chamber for generating a positive pressure and a second chamber for depositing a substrate as another embodiment according to the present invention.

As shown in FIG. 9, in order to maximize the positive pressure effect, a positive pressure generating unit (first chamber) 200 and a deposition unit (second chamber) 300 were separately installed, and an open shutter 250 was connected therebetween. . When the precursor-solvent is introduced into the closed space of the first chamber 200 and the solvent is evaporated, the pressure may be at least 2-3 times higher than the inside of the reactor 10 of FIG. 1. Thereafter, when the shutter 250 installed at the lower end of the first chamber 200 is momentarily opened, various thin films may be manufactured on the substrate while generating a strong and uniform flow to the lower end of the second chamber 300, that is, the substrate.

10 is a view showing a schematic diagram of a positive pressure coating device in which an exhaust pipe is installed in a portion of a lower portion of a reactor according to another embodiment of the present invention. Referring to Figure 10, in order to maximize the positive pressure effect of the present invention by further installing an exhaust pipe 15 in the lower portion of the reaction vessel 10 to give a uniform suction (105) from the lower end of the reaction vessel 10 local pressure The difference can be made further, showing that uniform coatings can be efficiently carried out in very small amounts. At this time, it is possible to adjust the pressure and the amount of the upper end through the flow control unit 70 mounted on the upper side of the reactor 10 at the same time.

11 and 12 are views showing a positive pressure coating apparatus capable of continuously performing a coating process as another embodiment of the present invention. As shown in Figs. 11 and 12, in this apparatus, the substrate is continuously moved by the conveyor, i.e., it enters the deposition section from the substrate preheating section and the positive pressure coating is performed. After that, it was moved to the thin film post-treatment unit, whereby heat treatment and gas treatment could be performed.

In this way, by providing a device capable of continuous processing, the process time is shortened, mass production process is possible, and the substrate preheating unit and the deposition unit are separated, so that the process stability and coating have significant advantages in terms of uniformity. The thin film can be realized.

Hereinafter, an embodiment of the coated thin film according to the type and amount of the precursor using the positive pressure coating method and the apparatus according to the present invention will be described in detail.

Example 1

FIG. 13 is an SEM image of the resulting WO ₃ thin film when W (CO) ₆ was mixed with cyclohexane reagent at 30% (solubility about 10%) and discharged into the reactor through a micro tube using a micro pump.

Cyclohexane is all evaporated at low temperature resulting in a first pressure increase, and then all W (CO) ₆ molecules are vaporized all around about 200 degrees, so that all precursors are mixed gas mists of gaseous cyclohexane-W (CO) ₆ . . The liquid-vapor phase change is a change in volume caused by the ascending air current created in the considerably larger one to wind shear allows the WO ₃ thin film production.

For reference, the thin film is a material widely known as an electrochromic material and showed good physical properties. This process corresponds to the upper figure of FIG. In the case of introducing the liquid precursor, when gas is flowed into the microtube in the apparatus of FIG. 5, it is possible to prevent the aggregation of the discharged microdroplets and reduce the size of the microdroplets. Other metal carbonyls such as Mo (CO) 6 show the same result. The total amount of droplets into the injected precursor mite is 5 ml. The substrate temperature is 300 degrees. The device used is FIG. 1.

Example 2

FIG. 14 is a solution using SnCl ₄ 5H ₂ O and ethylene glycol (ethylene glycol) using the apparatus of FIG. 9, and coated with precursor microdroplets mixed with ethanol and distilled water 2: 1 as a solvent. SEM image of the thin film.

Ethylene glycol is partially vaporized after the solvent is vaporized, which helps to increase the partial pressure. The remainder is a solid phase complexed or modified with the raw material reagent and destructively evaporates at a temperature of 200 degrees or more. At this time, the solid precursor in the evaporated state of the solvent is broken to make the precursors fine. This corresponds to the lower process of FIG. The total amount injected is 2 ml and the substrate temperature is 500 degrees.

Example 3

15 is a solution using SnCl ₄ 5H ₂ O, NH ₄ F, ethylene glycol (ethylene glycol) using the apparatus of Figure 10, the solvent was coated with a precursor microdroplets mixed with ethanol and distilled water Thin film SEM picture. NH ₄ F synthesized the coating solution so that the F / Sn ratio is 0.15 ratio. The result was a fluorine-doped tin oxide (FTO) transparent conductive film. The total amount of microdroplets injected is 2 ml and the substrate temperature is 500 degrees.

Example 4

FIG. 16 is a SEM photograph showing thin film growth behavior according to the amount of precursor introduced into the reactor using the apparatus of FIG. 1 and using the solution of Example 3. FIG. As the amount of precursor introduced increased, the thickness of the thin film increased. Interestingly, the grain size growth in the thin film was markedly increased by the film thickness growth, and vertical grain growth was observed in the cross-sectional photograph. This clearly shows the effect of increasing the positive pressure according to the increase of the amount introduced in the present invention, in addition to the simple meaning that the thickness of the thin film is simply increased as the amount continuously introduced.

In other words, increasing the amount of introduction maximizes the local positive pressure (FIGS. 2-4) and generates a strong precursor flow over the substrate. At the same time, many precursors collect on the substrate and help to grow with large grains. Introduction of the about 1 ml precursor resulted in a thin film about 150 nm thick, and introduction of the about 3 ml precursor resulted in a thin film about 450 nm thick. In contrast to the simple proportionality of the film thickness, the grain size increased by three to five times. It also showed a decrease in the electrical potential. The substrate temperature was 500 and the apparatus of FIG. 1 was used. And, Figure 17 is a SEM photograph of the TiO2 thin film coated using a positive pressure coating apparatus according to the present invention.

In addition, the TiO2 thin film was obtained when the organometallic reagent was made of Ti-Cl in the composition of Example 2. The substrate temperature is 500 degrees and the amount of precursor introduced is 10 ml. The apparatus used was FIG. 11 and an Al 2 O 3 deposit was obtained when the organometallic reagent was Al-Cl based in the composition of Example 2. The substrate temperature is 500 degrees and the amount of precursor introduced is 10 ml. The device used is FIG. 11.

In the present invention as described above has been described by the specific embodiments, such as specific components and limited embodiments and drawings, but this is provided to help a more general understanding of the present invention, the present invention is not limited to the above embodiments. For those skilled in the art, various modifications and variations are possible from these descriptions.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and all the things that are equivalent to or equivalent to the claims as well as the following claims will belong to the scope of the present invention. .

When the present invention is provided, the solvent and the additives vaporized in the coating reagent-solvent system induce localized high pressure or positive pressure, thereby allowing the precursor complexes to naturally move to the substrate, thereby facilitating thin film production.

In addition, expensive equipment necessary for a ceramic thin film including a transparent conductive film, that is, high vacuum equipment is not required, so that various ceramic thin films can be easily provided and a method that can be continuously processed can reduce the manufacturing cost, thereby enabling mass production.

Claims (19)

(a) heating the substrate located at the lower end of the integrated reactor; (b) injecting a precursor of a deposition material component into the reactor through at least one sprayer on an upper end of the integrated reactor; And and (c) inverting the pressure distribution inside the reactor as the precursor descends to the substrate, thereby depositing an atomized precursor on the substrate. (a) heating a substrate located at the lower end of the second chamber of the integrated reactor in which the first chamber and the second chamber are divided up and down; (b) injecting a precursor of a deposition material component into the first chamber in a predetermined amount through the at least one sprayer in the upper end of the first chamber; (c) discharging the precursor inside the first chamber into the second chamber through opening of at least one shutter disposed between the first chamber and the second chamber; And (c) depositing the discharged precursor on the substrate. The method according to claim 1 or 2, Positive pressure coating method characterized in that the exhaust pipe is provided in at least a portion of the reaction vessel located below the substrate to control the positive pressure and the concentration of the precursor locally generated. The method according to claim 1 or 2, And the precursor is used as at least one of a liquid reagent-solvent and a solid reagent-solvent. delete delete The method according to claim 1 or 2, Positive pressure coating method characterized in that the deposition material component is an organometallic compound containing at least one chlorine (Cl) ligand. The method according to claim 1 or 2, Positive deposition coating method characterized in that the deposition material component is an organometallic compound containing at least one carbon monooxide (carbon monooxide) ligand. The method according to claim 1 or 2, Positive pressure coating method, characterized in that the introduction of the precursor through the spray into the reaction vessel using a ceramic tube having an internal diameter of at least 1μm to 50μm. The method according to claim 1 or 2, Positive pressure coating method characterized in that to connect the gas pipe to the injection unit and the precursor to the inside of the reactor simultaneously with the gas. The method according to claim 1 or 2, Positive pressure coating method, characterized in that the precursor is in the form of a sol or gel solution. A reactor for reacting the precursor of the deposition material component to generate a positive pressure; A substrate positioner positioned at a lower end of the reactor; At least one spraying unit discharging the precursor into an upper portion of the reactor to enable deposition on the substrate; And Positive pressure coating device comprising a flow rate control unit for controlling any one of the flow rate of the precursor introduced into the reaction tank and the pressure in the reaction tank on the reaction tank side. A first chamber positioned above the integrated reactor to generate a positive pressure by reacting a precursor of the deposition material component; A second chamber disposed under the reactor to deposit a substrate; An injection unit for discharging the precursor into the first chamber; A substrate positioner for positioning the substrate at a lower end of the second chamber, Positive pressure coating apparatus, characterized in that the first chamber and the second chamber is connected by at least one shutter. The method according to claim 12 or 13, The substrate position portion positive pressure coating apparatus, characterized in that it comprises a heater for heating the substrate and a driving device to enable the vertical movement of the substrate. The method according to claim 12 or 13, Further comprising a substrate preheater for preheating the substrate and a post-treatment for post-treatment of the coated substrate on the outer side of the lower end of the reactor, The substrate preheating unit, the substrate position portion and the post-processing portion is connected to a conveyor belt positive pressure coating apparatus, characterized in that the continuous movement of the substrate. The method according to claim 12 or 13, The spraying device is a positive pressure coating, characterized in that the injection portion made of a ceramic tube having an internal diameter of at least 1μm to 50μm. The method according to claim 12 or 13, Positive pressure coating device, characterized in that for further connecting a gas pipe for injecting gas into the injection unit. The method according to claim 12 or 13, Located on the upper side of the reaction vessel is installed so as to be rotatable, positive pressure coating device, characterized in that it further comprises an auxiliary injection for introducing the precursor into the reactor. The method according to claim 12 or 13, Positive pressure coating device, characterized in that the exhaust pipe is provided in at least a portion of the reaction vessel located below the substrate to control the positive pressure and the concentration of the precursor locally generated.

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