KR20160140282A - Nozzle for spray pyrolysis deposion and device for forming a thin film having the same - Google Patents

Abstract

The present invention relates to a nozzle for forming a thin film and a device for forming a thin film. The present invention is to provide a nozzle for forming an even compound thin film to correspond to area expansion of a substrate using two kinds of liquid drop streams including different source precursors. According to an embodiment of the present invention, the nozzle includes: a core nozzle including a first inlet connected to a first supply path and a first outlet, wherein a first liquid drop stream containing a first source precursor transferred from the first supply path flows into the first inlet, and the first outlet injects the first liquid drop stream flowing inside; and a shell nozzle including a second inlet connected to a second supply path, a second outlet injecting a second liquid drop stream flowing inside, and a mixing cavity accommodating the first outlet of the core nozzle between the second inlet and the second outlet, wherein the second liquid drop stream containing a second source precursor transferred from the second supply path flows into the second inlet.

Description

TECHNICAL FIELD The present invention relates to a nozzle for spray pyrolysis deposition and a thin film forming apparatus including the nozzle for spray pyrolysis deposition.

The present invention relates to a thin film deposition technique, and more particularly, to a nozzle for spray pyrolytic deposition and a thin film forming apparatus including the same.

BACKGROUND ART [0002] In a solar cell, a liquid crystal display, an organic light emitting display (OLED), or a plasma display device, a substrate in which a transparent conductive film is formed on a transparent substrate such as a glass substrate which is an insulator is widely used. Conductive metal oxides such as indium tin oxide (ITO), tin oxide, or fluorine-doped tin oxide (FTO) are typically used for the transparent conductive film. Of these oxides, the transparent conductive film containing ITO as a main component has been widely applied not only to display devices of personal computers, televisions, and digital signage but also to touch panels.

In recent years, there has been an attempt to heat or heat a resistive transparent conductive film by applying electrical energy directly to the conventional fossil fuel as a high-efficiency and environment-friendly technology for meeting the carbon suppression policy. For example, the transparent conductive film may be used as a glasshouse for agriculture and livestock facilities such as a vinyl house or an animal husbandry facility, or as a heating source for a food processing facility, or for preventing condensation or icing of buildings, automobiles, Film is being applied.

Among the above-mentioned applications, the FTO conductive film described above has high transparency, has almost no resistance change to 600 DEG C, is excellent in chemical resistance and abrasion resistance, and is suitable for harsh external environments. Therefore, , And is attracting attention as a heating element for heating. The FTO conductive film is generally formed by a vapor deposition method such as chemical vapor deposition (CVD), atomic layer deposition (ALD), or organic vapor deposition (OVPD or condensation coating).

However, since the substrate such as the window glass has various sizes or a large area and has various shapes such as a plate shape or a curved shape depending on its application, it is difficult to realize the designed characteristics by the vapor deposition method described above . For this reason, there is a need for a thin film forming apparatus capable of uniform deposition on a large area substrate by droplet spraying. As an alternative technique, there is a spray pyrolysis deposition method in which a transparent conductive film is coated by a droplet spraying method. The spray pyrolytic deposition method uses a source solution comprising at least one source precursor containing a composition of the thin film to form a thin film and a solvent for dissolving or dispersing the source precursor as a raw material for thin film formation. However, when the number of the precursors is more than 2, a suitable solvent may be required for each precursor, and if the physical properties of these solvents are remarkable, there is a problem that a uniform thin film of the compound can not be finally obtained over the entire large-area substrate.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a nozzle capable of forming a homogeneous compound thin film in correspondence to the large-sized substrate by using two or more types of droplet streams containing different source precursors.

Another object of the present invention is to provide a thin film forming apparatus including a nozzle having the above-described advantages.

The nozzle for solving the above-mentioned problem is provided with a first inlet connected to a first supply passage and into which a first droplet stream containing a first source precursor transferred from the first supply passage is drawn, A core nozzle including a first outlet for spraying; And a second outlet connected to the second supply passage for introducing a second droplet stream containing a second source precursor transferred from the second supply passage and a second outlet for injecting the drawn second droplet stream, And a mixing cavity for receiving the first outlet of the core nozzle between the second inlet and the second outlet.

A second source precursor for dissolving or dispersing the first source precursor of the first droplet stream in the first droplet stream and a second solvent precursor for dissolving or dispersing the second source precursor of the second droplet stream in the second droplet stream, Solvents can be of different kinds of solvents. The first solvent and the second solvent may have a specific gravity, a degree of hydrophilicity, or both of them may be different. The first and second solvents may be any one of alcohol and water.

According to another aspect of the present invention, there is provided a thin film forming apparatus for forming a thin film on a surface of an object to be processed by a spray pyrolysis method, comprising: support means for placing the object to be processed; And a nozzle for spraying the droplet stream on one surface of the object to be treated. The nozzle is characterized in that the nozzle comprises a first inlet connected to a first supply passage and into which a first droplet stream containing a first source precursor delivered from the first supply passage is drawn, A core nozzle comprising a first outlet for making a first outlet; And a second outlet connected to the second supply passage for introducing a second droplet stream containing a second source precursor transferred from the second supply passage and a second outlet for injecting the drawn second droplet stream, And a mixing cavity for receiving the first outlet of the core nozzle between the second inlet and the second outlet.

In one embodiment, at least one of the core nozzle and the shell nozzle may be a diffusion nozzle. The thin film may comprise a heating layer comprising fluorine doped tin oxide.

According to an embodiment of the present invention, the nozzle has a structure of a shell nozzle having a core nozzle and a mixing cavity surrounding the outlet of the core nozzle, thereby inducing uniform mixing of the source solvent droplets to which different solvents are applied, A nozzle capable of uniformly forming a thin film of a compound containing two or more components on the surface of the substrate can be provided.

Further, according to the embodiment of the present invention, a thin film forming apparatus using the nozzle having the above advantage can be provided.

1 shows a thin film forming apparatus according to an embodiment of the present invention.
FIG. 2A is a perspective view of a nozzle of FIG. 2A, and FIG. 2C is a perspective view illustrating a nozzle according to another embodiment of the present invention.

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

The embodiments of the present invention are described in order to more fully explain the present invention to those skilled in the art, and the following embodiments may be modified into various other forms, The present invention is not limited to the embodiment. Rather, these embodiments are provided so that this disclosure will be more faithful and complete, and will fully convey the scope of the invention to those skilled in the art.

In the following drawings, thickness and size of each layer are exaggerated for convenience and clarity of description, and the same reference numerals denote the same elements in the drawings. As used herein, the term "and / or" includes any and all combinations of any of the listed items.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a," "an," and "the" include singular forms unless the context clearly dictates otherwise. Also, " comprise "and / or" comprising "when used herein should be interpreted as specifying the presence of stated shapes, numbers, steps, operations, elements, elements, and / And does not preclude the presence or addition of one or more other features, integers, operations, elements, elements, and / or groups.

Although the terms first, second, etc. are used herein to describe various elements, components, regions, layers and / or portions, these members, components, regions, layers and / It is obvious that no. These terms are only used to distinguish one member, component, region, layer or section from another region, layer or section. Thus, a first member, component, region, layer or section described below may refer to a second member, component, region, layer or section without departing from the teachings of the present invention.

A thin film forming apparatus according to an embodiment of the present invention, and more particularly, a device for forming a transparent conductive film, may be based on spray pyrolysis deposition (SPD). The spray pyrolysis method is a spray pyrolysis method in which a liquid droplet containing a raw material compound produced by using a spraying means such as an atomizer is sprayed so that the solvent contained in the liquid droplet is evaporated, (In this specification, these intermediate products are collectively referred to as a " gas phase "), while carrying out at least one or two or more steps of the reaction between the carrier gas and the precursor (for example, oxidation or reduction reaction) Precursors), and a thin film is formed on an object to be processed which has been heated up to a deposition temperature in advance by a vapor precursor discharged through the liquid transfer path. A crystalline (e.g., polycrystalline) thin film, nanorod, nanowire, or amorphous film growth can be achieved through the deposition mechanism.

The following embodiments are directed to optimizing the thin film formation based on the SPD method (or SPD deposition) so as to economically and easily form a thin film having uniform characteristics on a workpiece having various areas and shapes such as a window glass And a thin film forming apparatus including the nozzle.

1 shows a thin film forming apparatus 100 according to an embodiment of the present invention.

Referring to FIG. 1, the thin film forming apparatus 100 forms a thin film on one surface SA of the workpiece DP by the SPD method. The object to be processed (DP) is a substrate such as glass, ceramics, semiconductor, or metal, which is illustrative and the present invention is not limited thereto. In addition, the surface SA of the workpiece DP may include smooth or embossed patterns such as embossing.

The thin film forming apparatus 100 includes a reaction chamber 10 for SPD deposition, a droplet generating chamber 20 for generating droplets containing a precursor for thin film deposition; A carrier gas supply unit 30 for supplying a carrier gas for transferring the generated droplets to the reaction chamber 10; And a supply passage (50) for transferring the droplet contained in the carrier gas to the nozzle (40).

The reaction space of the reaction chamber 10 is defined by the chamber wall CW and the chamber wall CW has a suitable structure for insulation, sealing and / or isolation from the outside. In another embodiment, the chamber wall CW may be a hood. The hood can maintain atmospheric pressure conditions in the reaction space while preventing heat from flowing out of the reaction space to the outside at the time of film deposition and wasting the liquid droplets to the outside.

The structure of the reaction chamber 10 may have a structure suitable for coating the object to be treated PS, for example, a circular structure or a rectangular structure, and any other structure. The reaction chamber 10 may be provided with a suitable heating means such as an induction heating coil, a resistance wire, or a halogen lamp around the reaction chamber 10 to provide a reaction space where the droplet is dried and pyrolyzed.

The supporting means CH may be provided in the reaction chamber 10 for holding the objects to be treated PS and the supporting means CH preferably is a resistance heater for controlling the temperature of the object to be treated PS, Fluidized heating and / or air cooled, water cooled or semiconductor cooled cooling means. To this end, the support means CH can be made of aluminum, graphite, alumina or aluminum nitride as a non-limiting example to prevent deformation such as banding of the object PS having a good thermal conductivity. Further, the supporting means CH may include any one of a lift pin, an electrostatic chuck, and a vacuum chuck, or a combination thereof, and may be provided with a feature for uniform film formation during the thin film forming process for the object to be processed PS It is possible to rotate the ligatures PS.

In the reaction chamber 10, a nozzle 40 for spraying the droplet is provided on the workpiece DP. The nozzle 40 is connected to the supply passage 50, and receives the droplet stream to jet it onto the object to be processed DP. The nozzle 40 and the supply passage 50 are separately described in detail later. In some embodiments, the reaction chamber 10 may further be provided with a collector (see CE in FIG. 4) connected with a vacuum pump to remove reaction byproducts and residual precursors after reaction.

The droplet generating chamber 20 may be provided with a starting solution containing a suitable starting compound and an energy source (not shown) for forming droplets from the surface of the starting solution. The energy source may be a device for applying mechanical energy such as an ultrasonic vibrator having a predetermined frequency such as 1.65 MHz, or may be a thermal evaporation device.

The droplet generated from the starting solution serves as a reaction vessel, and the particle growth generated can be limited to within the secondary growth, so that particles having a uniform particle size can be obtained. The size of the droplet depends on the surface tension, density and frequency of the starting solution, and the size and size distribution of the particle size may be controlled by adjusting the concentration of the starting solution. In some embodiments, appropriate screening control may be performed for particle size selection.

The droplet generating chamber 20 may be composed of two or more containers. In each vessel, a source precursor for forming a thin film and a solvent for dissolving or dispersing it may be contained, and the solvents added to the respective vessels are different kinds of solvents. For example, the droplet generating chamber 20 may include first and second containers. The first container may receive a first solvent that dissolves or disperses a first source precursor and the first source precursor from which first droplets containing a first source precursor may be generated. The second vessel may contain a second source precursor and a second solvent that dissolves or disperses the second source precursor, from which second droplets containing a second source precursor may be generated.

If the first source precursor and the second source precursor are different kinds of compounds, for spray pyrolytic deposition, the solvent for the first source precursor and the solvent for the second source precursor may be of different kinds. For example, if the first source precursor is a metal compound, the first solvent may be water, and if the second source precursor is a fluorine compound containing doping elements, such as fluorine, the second solvent may be an alcohol A second source solution comprising the first source precursor and the first solvent and a second source solution comprising the second source precursor and the second solvent may be required since the solvents are different. Further, the first container for accommodating the first source solution and the second container for accommodating the second source solution may be required.

The first container and the second container constitute a droplet generating chamber 20 and are independently connected to a carrier gas supply unit 30 so that a carrier gas is supplied to the first and second containers, The first and second droplets generated in the carrier gas supply portion are loaded into the carrier gas supplied from the carrier gas supply portion to form the first droplet stream and the second droplet stream. These droplet streams will be delivered to the nozzle 40 through the first and second supply channels 50, respectively, which will be described later.

The carrier gas supply unit 30 coupled to the droplet generating chamber 20 may have a valve system and a mass flow controller (MFC) that controls the supply flow rate of the carrier gas. The carrier gas is delivered to the reaction chamber 10 via the droplet generating chamber 20 and the carrier gas serves to push the first droplet and the second droplet to the nozzle 40, 50 from being adsorbed by the inner wall of the inner wall of the inner wall of the inner wall of the inner wall.

The carrier gas may be a reactive gas such as oxygen, ozone, hydrogen or ammonia, an inert gas such as helium or argon, or a mixed gas thereof, but the present invention is not limited thereto. For example, the carrier gas may be air.

2A shows a supply channel 50 and a nozzle 40 according to an embodiment of the present invention. FIG. 2B is a perspective view of the nozzle 40 of FIG. 2A, and FIG. 2C is a cross- Is a perspective view showing the nozzle 40 '.

Referring to FIG. 2A, the droplet generating chamber 20 may include a first container 20A containing a first source solution 21a and a second container 20B containing a second source solution. In another embodiment, a third container (not shown) may be further provided if a third source solution is desired.

The first container 20A and the second container constitute the droplet generating chamber 20 and the carrier gas supply unit 30 is connected independently so that carrier gas is supplied to the first and second containers, The first and second droplets produced in the two vessels are loaded into the carrier gas fed from the carrier gas supply to form a first droplet stream A and a second droplet stream B. These droplet streams A and B will be delivered to the nozzle 40 through the first and second supply channels 50, respectively, which will be described later.

Referring to FIG. 2B together with FIG. 2A, the nozzle 40 may include a core nozzle 40A and a shell nozzle 40B. The core nozzle 40B is connected to the first supply passage 50A and includes a first inlet 40A_1 through which the first droplet stream A is introduced and a first outlet 40A through which the first droplet stream A ' 40_2). The shell nozzle 40B_2 is connected to the second supply passage 50B to receive the second inlet 40B_1 into which the second droplet stream B is introduced and the first outlet 40A_2 of the shell nozzle 40A inside A mixing cavity 40B_3 in which the injected first droplet stream A 'and the drawn second droplet stream B' are mixed, and a second outlet injecting the mixed first and second droplet streams C And a shell nozzle 40B including a shell nozzle 40B_2.

The present invention is not limited thereto and the structure of the core nozzle 40A in the mixing cavity 40B_3 of the shell nozzle 40B is not limited to the structure in which the core nozzle 40A is disposed in the shell nozzle 40B, And may have any structure in which the first outlet 40A_2 of the nozzle 40A can be arranged.

The first inlet 40A_1 and the second inlet 40B_1 may have any cross sectional structure such as a circle or a square having a concentric structure, but the present invention is not limited thereto. For example, the first inlets 40A_1 may be disposed eccentrically in the second inlet 40B_1 or may be disposed at different positions, respectively.

The shape of the first outlet 40A_1 may have a plurality of holes that are slit or perforated. The first droplet stream A 'ejected from the first outlet 40A_1 is mixed with the second droplet stream B' drawn into the shell nozzle 40B in the mixing cavity 40B_3. The mixing cavity 40B_3 may include any shape, volume, or structure therein that can induce mixing between these streams. The first droplet stream A 'and the second droplet stream B' thus mixed are passed through the second outlet 40B_2 of the shell nozzle 40B to form a single stream of uniformly mixed first and second droplets (C).

The shapes of the core nozzle 40A and the shell nozzle 40B are in the form of loudspeakers that expand toward the respective outlets 40A_2 and 40B_2 to induce diffusion of the streams as shown in FIG. 2B, but this is exemplary, But is not limited thereto. For example, as shown in Fig. 2C, a nozzle 40 'in which the core nozzle 40A and the shell nozzle 40B are in the form of a cylinder may be provided. In another embodiment, the shapes of the core nozzle 40A and the shell nozzle 40B may be different from each other, and the shape of the core nozzle 40A may be modified to facilitate mixing between the streams in the mixing cavity 40B_3 will be.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Will be clear to those who have knowledge of.

Claims (8)

And a first outlet connected to the first supply flow path for injecting a first droplet stream containing a first source precursor transferred from the first supply flow path and a first outlet for injecting the drawn first droplet stream, Nozzle; And
A second inlet connected to a second supply passage for introducing a second droplet stream containing a second source precursor transferred from the second supply passage and a second outlet for injecting the drawn second droplet stream, And a mixing cavity for receiving the first outlet of the core nozzle between the second inlet and the second outlet. The method according to claim 1,
A second source precursor for dissolving or dispersing the first source precursor of the first droplet stream in the first droplet stream and a second solvent precursor for dissolving or dispersing the second source precursor of the second droplet stream in the second droplet stream, The solvent is a different kind of solvent. 3. The method of claim 2,
Wherein the first solvent and the second solvent have specific gravity, hydrophilicity, or both are different solvents. 3. The method of claim 2,
Wherein the first and second solvents are any one of alcohol and water, respectively. Supporting means for placing said object to be processed; And
And a nozzle for spraying a droplet stream on one surface of the object to be processed,
The nozzle
And a first outlet connected to the first supply flow path for injecting a first droplet stream containing a first source precursor transferred from the first supply flow path and a first outlet for injecting the drawn first droplet stream, Nozzle; And
A second inlet connected to a second supply passage for introducing a second droplet stream containing a second source precursor transferred from the second supply passage and a second outlet for injecting the drawn second droplet stream, And a mixing cavity for receiving the first outlet of the core nozzle between the second inlet and the second outlet. 6. The method of claim 5,
Wherein at least one of the core nozzle and the shell nozzle is a diffusion nozzle. 6. The method of claim 5,
Wherein the thin film comprises a heating layer comprising fluorine-doped tin oxide. 6. The method of claim 5,
A thin film forming apparatus for forming a thin film on one surface of an object to be processed by spray pyrolysis, the thin film forming apparatus performing an in-line or batch type process.

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