KR101839077B1 - Spray pyrolysis deposition device having twin nozzles - Google Patents

Abstract

The present invention relates to a spray pyrolysis apparatus having a double nozzle. The apparatus for forming an in-line spray pyrolysis thin film according to an embodiment of the present invention includes a support apparatus for supporting and transporting a substrate, a first nozzle for defining a first deposition region by providing a first precursor stream in a reverse direction with respect to the transport direction of the substrate, A second nozzle unit disposed at a rear side of the first nozzle unit with respect to the transport direction of the substrate and defining a second deposition area by providing a second precursor stream in a forward direction with respect to the transport direction of the substrate, 1 deposition zone and the second deposition zone.

Description

[0001] Spray pyrolysis deposition device having twin nozzles [

The present invention relates to a thin film forming apparatus, and more particularly, to a spray pyrolysis apparatus having a double nozzle.

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. As the transparent conductive film, a conductive metal oxide such as tin-doped indium oxide (ITO), tin oxide, or fluorine-doped tin oxide (FTO) is typical. Among these oxides, the transparent conductive film containing ITO as a main component is widely used as a display device of a personal computer, a television, and a digital signage.

In recent years, there has been an attempt to apply a transparent conductive film for resistance heating by direct electrical energy instead of conventional fossil fuels as a carbon-suppressing policy and an environmentally friendly technology for energy saving. For example, there has been an attempt to apply a transparent conductive film in place of the fossil fuel used in conventional heating / dehumidification / heat treatment (processing). Typically, a transparent conductive film is used as a heating source of a vinyl house, a glasshouse of a livestock breeding facility, or a food processing facility, or as a heating resistor for preventing condensation or icing on a window glass of a building, an automobile or an aircraft .

The transparent 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). These conventional methods for forming a transparent conductive film are not easy to control the thin film structure for improving the performance of the transparent conductive film and are difficult to form two or more complex structures in the prepared transparent conductive film and are therefore applicable to various application devices using the transparent conductive film . In addition, the above-described conventional deposition method has a problem that an expensive process is required because a thin film is formed in a vacuum.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method of manufacturing a thin film, which can improve the economical efficiency of a thin film forming process, facilitate control of a thin film structure in a single thin film forming process, The present invention provides an in-line spray pyrolytic thin film forming apparatus that can be implemented in a forming process.

Another technical problem to be solved by the present invention is to provide a method of forming an in-spray pyrolysis thin film having the above-described advantages.

According to an aspect of the present invention, there is provided an apparatus for forming an in-line spray pyrolysis thin film, comprising: a support apparatus for supporting and transporting a substrate; a first precursor stream provided in a direction opposite to a transport direction of the substrate, A first nozzle portion defining a first deposition region and a second nozzle region defining a second deposition region by providing a second precursor stream in a forward direction with respect to a transport direction of the substrate, 2 nozzle portion and a deposition transition region between the first deposition region and the second deposition region.

In one embodiment, the support device may include a heater for heating the substrate. The film-forming transfer region may not be provided with the first precursor stream and the second precursor stream. In one embodiment, reaction conditions for forming a uniform fine pattern on the substrate may be formed within the film-forming transfer region.

In one embodiment, the substrate may be annealed, stress relieved to prevent cracking, crystallization of the resulting nuclei, or nucleation. In one embodiment, the apparatus further includes a first exhaust unit disposed in front of the first nozzle unit with respect to a conveyance direction of the substrate, and a second exhaust unit disposed behind the second nozzle unit with respect to the conveying direction of the substrate can do.

In one embodiment, the first precursor stream and the second precursor stream may comprise the same precursor. In another embodiment, the first precursor stream and the second precursor stream may comprise different precursors.

In one embodiment, the angle of spray of the first precursor stream and the second precursor stream can be controlled. In one embodiment, the spray angle of the first precursor stream and the second precursor stream may be symmetrically adjusted with respect to the vertical direction of the substrate.

In one embodiment, the precursor solution mixed with the second tin (SnCl ₄ .5H ₂ O), ammonium fluoride (NH ₄ F) and solvent is supplied through the first nozzle portion and the second nozzle portion, A fluorine doped tin oxide film may be formed. In one embodiment, the temperature of the deposition transition zone may be higher than 200 ° C and less than 600 ° C.

According to another aspect of the present invention, there is provided a method of forming an in-line spray pyrolysis thin film, comprising: providing a substrate on a support device capable of transferring a substrate; During the transfer of the substrate, it may undergo a first deposition step of providing a first precursor stream in a direction reverse to the transport direction of the substrate. After the first depositing step, a deposition step may be performed to form a reaction condition for forming a fine pattern from the first deposit formed in the first depositing step. After the deposition transition step, a second deposition step may be performed during which the substrate is transported, providing a second precursor stream in a forward direction with respect to the transport direction of the substrate.

In one embodiment, the first precursor stream and the second precursor stream may be provided by nozzle portions having at least one or more nozzles. In one embodiment, the support device may include a heater for heating the substrate.

In one embodiment, the deposition transition step may not provide a precursor stream for a predetermined time. Further, in the film formation transfer step, the substrate may be annealed, the stress may be released to prevent cracks, crystallization of the generated nuclei, and nucleation.

In one embodiment, it may undergo a first evacuation step of evacuating the byproducts generated in the first deposition step. And a second evacuation step of evacuating the byproducts generated in the second deposition step.

In one embodiment, the first precursor stream and the second precursor stream may comprise the same precursor. In another embodiment, the first precursor stream and the second precursor stream may comprise different precursors.

In one embodiment, the first precursor stream and the second precursor stream can be adjusted in dispense angle by the nozzle portions. The dispense angle of the first precursor stream and the second precursor stream may be symmetrically adjusted with respect to the vertical direction of the substrate.

In one embodiment, the first precursor or the second precursor stream stream may include stannic chloride _{(SnCl 4 · 5H 2 0)} , ammonium fluoride (NH ₄ F) and a solvent. In one embodiment, the film-forming transfer step may be performed at a temperature higher than 200 ° C and less than 600 ° C.

In one embodiment, after the substrate is provided, the substrate may be further subjected to a surface treatment. In one embodiment, the substrate may be further quenched and cooled.

According to an embodiment of the present invention, an apparatus for forming an in-line spray pyrolysis thin film includes a first nozzle unit for providing a first precursor stream in a reverse direction to a transport direction of a substrate, and a second nozzle unit for supplying a second precursor stream in a forward direction with respect to the transport direction of the substrate A film formation transfer zone in which the precursor stream is not provided between the first nozzle unit and the second nozzle unit is defined and the thin film structure is controlled by a combination of the reverse and forward streams And the nucleation or grain growth can be ensured by the film forming transition region and any intermediate thin film structure can be formed before the film formation by the second precursor stream, Thereby forming a thin film.

In the film-forming transfer region, the substrate is released from the stress of the film deposited on the first nozzle portion, thereby preventing or reducing a crack in the film as the final product.

1 is a flowchart illustrating a method of forming an in-line spray pyrolysis thin film according to an embodiment of the present invention.
2A is a cross-sectional view illustrating an apparatus for forming an in-line spray pyrolysis thin film according to an embodiment of the present invention.
FIG. 2B is a perspective view of the nozzle portions of the apparatus for forming an in-line spray pyrolysis thin film of FIG. 2A. FIG.
3A is a cross-sectional view illustrating an apparatus for forming an in-line spray pyrolysis thin film according to another embodiment of the present invention.
FIG. 3B is a perspective view of the nozzle portions of the in-line spray pyrolytic film forming apparatus of FIG. 3A. FIG.
4A is a cross-sectional view illustrating an apparatus for forming an in-line spray pyrolysis thin film according to another embodiment of the present invention.
FIG. 4B is a perspective view of the nozzle portions of the in-line spray pyrolytic film forming apparatus of FIG. 4A. FIG.

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, It 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.

1 is a flowchart illustrating a method of forming an in-line spray pyrolysis thin film according to an embodiment of the present invention. 2A is a cross-sectional view showing an apparatus 1000 for forming an in-line spray pyrolysis thin film according to an embodiment of the present invention. FIG. 2B is a perspective view of the nozzle units according to one embodiment of the apparatus 1000 for forming an in-line spray pyrolysis thin film of FIG. 2A. The apparatus 1000 for forming an in-line spray pyrolysis thin film according to an embodiment of the present invention can be used in the method of forming an in-line spray pyrolysis thin film according to the embodiment of the present invention shown in Fig.

Referring to FIGS. 1 and 2A, at least one substrate SUB1 to SUB5 may be provided in the apparatus 1000 for forming an in-line spray pyrolysis thin film (S10). At least one substrate SUB1 to SUB5 may be provided to the in-line spray pyrolysis thin film forming apparatus 1000 at a constant distance or at a time interval.

The in-line spray pyrolysis thin film forming apparatus 1000 can form a thin film on one surface of the substrates SUB1 to SUB5. The substrates SUB1 to SUB5 are substrates such as glass, ceramics, semiconductors, or metals, which are illustrative and the present invention is not limited thereto. In addition, the surface of the substrate may include smooth or embossed patterns such as embossing. For example, the substrate may be one surface of a low-e glass or a heat-generating glass for forming a planar heating element, and it may be a substrate typically required to manufacture a large-area thin film.

In one embodiment, while the inline spray pyrolysis thin film is formed, the substrates SUB1 to SUB5 are transferred in one direction (A) to be transferred to the processing target SUB1, the target SUB2, the target SUB3, And can be provided as the treating object SUB4 and the treating object SUB5. The shapes of these objects may be the same or different. Fig. 2 illustrates a glass substrate in which the objects to be processed have the same shape.

The apparatus 1000 for forming an in-line spray pyrolysis thin film may include a supporting device CB installed in the reaction chamber CH, a first nozzle part 300A_1 and a second nozzle part 300A_2. 2A illustrates a dual nozzle structure composed of a first nozzle portion 300A_1 and a second nozzle portion 300A_2, but in another embodiment, the apparatus 1000 for forming an in-line spray pyrolysis thin film may have three or more nozzle portions . Reference numeral 100, 200, 400 and 500 illustrate a pretreatment unit, a first exhaust unit, a second exhaust unit, and a post-treatment unit, respectively, and the apparatus 1000 for forming an in-line spray pyrolysis thin film of the present invention further includes at least one .

The reaction space of the reaction chamber CH is defined by the chamber wall, and the chamber wall has a suitable structure for insulation, sealing or isolation from the outside. In another embodiment, the chamber wall may be a hood. The hood maintains the atmospheric pressure condition in the reaction space while preventing heat from flowing out from the inside of the reaction space to the outside at the time of film formation and wasting the liquid droplets to the outside. The chamber wall or hood may be made of a metal material made or coated with aluminum, stainless steel, copper or refractory metal and the like. For example, an anodized or ceramic coated material may be used for the metal material surface. As a further alternative, the chamber wall or hood may be wholly or partially made of an electrically insulating material such as quartz, ceramic, or the like.

The structure of the reaction chamber CH may have a structure suitable for coating the substrate, for example, a circular structure or a square structure, and any other structure. The reaction chamber may be provided with a suitable heater around it, such as an induction heating coil, a resistance wire, or a halogen lamp, to provide a reaction space where the droplet is dried and pyrolyzed.

In one embodiment, the reaction chamber CH is divided into a pretreatment zone PA, an exhaust zone EA1, a first deposition zone DA1, a film deposition transfer zone TA1, a second deposition zone DA2, The area EA2 and the post-processing area CA. The support device CB of the in-line spray pyrolysis thin film forming apparatus 1000 includes a transfer system such as a conveyor belt or roller device capable of transferring the substrate while coating a thin film on the surface. In one embodiment, the support apparatus CB supports the substrate and transports the substrate in one direction (A) so that the substrate is subjected to the processing steps PA, exhaust area EA1, first deposition area DA1, , The film deposition transfer area TA1, the second deposition area DA2, the exhaust area EA2, and the post-treatment area CA.

In another embodiment, a part of the support device CB of the in-line spray pyrolytic film forming apparatus 1000 may further include a heater for heating the substrate. The supporting device CB including the heater can not only heat the substrate but also support the substrate at the same time. The heater can be adjusted to maintain the same temperature or to have different temperatures in the respective regions described above.

The preprocessing unit 100 of the in-line spray pyrolytic film forming apparatus 1000 may define a preprocessing area PA where the substrate providing step S10 is performed. The pretreatment unit 100 can heat or modify the surface of the subject SUB1. In one embodiment, the pretreatment unit 100 may include a separate heater for heating the surface of the subject SUB1. The heater may be a halogen lamp, induction heating or hot wire, which is illustrative and not limiting. In another embodiment, the pretreatment unit 100 may include a plasma surface treatment apparatus that turns the substrate surface into an activated state and at the same time injects a reactive gas to form a new functional group using ion energy at the substrate surface. Thereafter, the subject SUB1 can be transferred in one direction (A) for movement to the next exhaust area EA1 or the first accumulation area DA1.

In one embodiment, the apparatus 1000 for forming an in-line spray pyrolysis thin film may be provided with a shutter or an air curtain separately for sealing and opening / closing between reaction chambers. For example, a shutter or an air curtain may be installed between the pretreatment unit 100 and the first exhaust unit 200.

In the apparatus 1000 for forming an in-line spray pyrolysis thin film, a first exhaust unit 200 may be installed at a rear end of the pretreatment unit 100. The first exhaust part 200 of the in-line spray pyrolytic film forming apparatus 1000 may define an exhaust area EA1 in which the first exhaust step S25 is performed. In one embodiment, the first exhaust part 200 may be disposed in front of the first nozzle part 300A_1 with respect to the conveying direction A of the substrate.

Also, in one embodiment, while the first deposition step S20 is performed by the substrate providing step S10 or the first nozzle part 300A_1 to be described later, the first exhaust part 200 performs the substrate providing step S10 , Or a by-product such as a reactant gas, a carrier gas, or an unreacted material (or unreacted gas) used or formed in the first deposition step S20 (S25).

In another embodiment, before the subject SUB2 on the support device CB undergoes the first deposition step S20 by the first nozzle portion 300A_1, the pre-processing region PA Or air or contaminants in the exhaust area EA1 may be discharged first through the first exhaust part 200. [

Referring to FIG. 2B together with FIG. 1, the object to be processed SUB2 transferred in one direction A is subjected to a first deposition step S20 in a first deposition area DA1 defined by the first nozzle part 300A_1, ≪ / RTI > The first nozzle portion 300A_1 sprays the first precursor stream PS1 onto the subject SUB2. The first nozzle unit 300A_1 may be coupled to at least one supply pipe PI1 for transferring the first precursor from the first material supply unit PP1 that generates and supplies the first precursor.

In one embodiment, the first nozzle portion 300A_1 for providing the first precursor stream PS1 includes a mixing portion for uniform mixing of the carrier gas with the first precursor delivered from the first feedstock supply portion PP1 And may include a spray hole or slit SL1 for spraying a uniformly mixed first precursor gas. 2B illustrates that the first nozzle unit 300A_1 and the second nozzle unit 300A_2, which will be described later, have a common mixing unit MP to share the mixing unit.

The first nozzle portion 300A_1 can provide the first precursor stream PS1 in a direction opposite to the transport direction A of the workpiece SUB2. To this end, in one embodiment, the injection hole or slit SL1 of the first nozzle unit 300A_1 may be provided in a direction opposite to the conveying direction A of the subject SUB2.

Similar to the first nozzle unit 300A_1, the second nozzle unit 300A_2 may include a second raw material supply unit PP2 for generating and supplying a second precursor and at least one supply pipe PI2. The second precursor may comprise a homogeneous or heterogeneous material as the first precursor. The second nozzle portion 300A_2 is connected to the second precursor stream PS2 for supplying the second precursor stream PS2 to the second nozzle portion 300A_2 for the uniform mixing of the carrier gas with the second precursor delivered from the second feedstock PP2. And a spray hole or slit SL2 for spraying a second precursor gas uniformly mixed with the mixing portion. The second nozzle unit 300A_2 may be used in the second deposition step S40. This will be described in detail later.

In one embodiment, the first precursor stream SP1 provided from the first nozzle portion 300A_1 is provided on the subject SUB2 to which the subject SUB1 is transferred in one direction A to form a first precursor stream SP1 on the subject SUB2 (S20). ≪ / RTI > In one embodiment, a first deposition area DA1 of a reaction chamber CH that provides a first precursor stream PS1 to a subject SUB2 may be defined. In one embodiment, the temperature of the first deposition area DA1 may be higher than 200 占 폚 and less than 400 占 폚.

The first precursor stream (PS1) comprises a droplet, an aerosol, or an intermediate product derived from the first precursor or the remaining precursor, wherein the first precursor is dissolved or dispersed in a small volume of solvent . In one embodiment, the first precursor stream PS1 may be for forming F-doped Tin Oxide (FTO). In this case, the first precursor is a chloride of tin as a tin precursor _{(SnCl 4 · 5H 2 O)} , (C 4 H 9) 2 Sn (CH 3 COO) 2, (CH 3) SnCl 3, (CH 3 ) ₂ SnCl ₂ , (CH ₃ ) ₃ SnCl ₁ or (C ₄ H ₉ ) ₃ SnH may be used and other precursors such as ((C ₄ H ₉ ) ₃ SnCl, (C ₄ H ₉ ) ₂ SnCl ₂ , or (C ₄ H ₉ ) SnCl ₃ ) may be used. Also, monobutyltin chloride, dibutyltin chloride or tributyltin chloride may be used as the tin precursor. These are illustrative, and the first precursor may include other tin-containing compounds as a precursor of tin. Also, the first precursor may be a fluorine-containing compound such as ammonium fluoride (NH ₄ F), CF ₃ Br, CF ₂ Cl ₂ , CH ₃ CClF ₂ , CF ₃ COOH, or CH ₃ CHF ₂ as a fluorine precursor And the present invention is not limited thereto. In one embodiment, the solvent may comprise distilled water or alcohol, and the present invention is not limited thereto.

The first raw material supply portion PP1 may be provided with a starting solution containing a suitable starting compound and an energy source (not shown) for forming droplets from the surface or interface 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.

At least one supply pipe PI1 may be a flow path for transferring the first raw material supply portion PP1 to the first deposition region DA1 of the reaction chamber CH. In one embodiment, the first precursor provided from the first precursor PP1 may be transferred through at least one or more supply pipes PI1 to provide a first precursor stream SP1 from the slit SL1.

If the first nozzle unit 300A_1 includes a single supply pipe, the thin film formation must be performed while moving the first nozzle unit 300A_1 uniformly on the surface of the object to be processed on a large area of the object to be processed. In this case, in the region where the return path takes place during the movement path of the single feed pipe, the time for which the nozzles of the single feed pipe remain is increased so that the thickness of the coated thin film is smaller than the thickness of the thin film formed in the region where the single feed pipe simply passes. It can be big. However, according to the embodiment of the present invention, by arranging the single supply pipes side by side and expanding a plurality of them, it is possible to form a thin film having a uniform thickness on a large-area workpiece, It is possible to implement a continuous pattern without any dust.

At least one of the supply pipes PI1 may be formed of a metal conduit or a quartz conduit such as stainless steel having suitable heat resistance so as to be externally heated. In some embodiments, the inner surface of at least one of the supply pipes PI1 may be coated with a Teflon coating or a water repellent coating to prevent adhesion, in order to improve chemical resistance and corrosion resistance. The heating of the supply pipes PI1 may be performed by resistive heating in which a resistance wire is wrapped around the outside of the conduit or radiant heating such as a halogen lamp. Although not shown, the supply pipes PI1 may be installed in a separate housing for isolation from the outside.

Preferably, the at least one supply pipes PI1 may have a suitable temperature control system for individually adjusting the temperature of the first precursor stream SP1 therein, for each supply pipe. In this case, a resistance heating method in which the resistance wire is wrapped around the outside of each supply pipe and the amount of electric power to be supplied can be individually adjusted for each flow channel may be advantageous. However, it should be understood that this individual adjustment does not preclude the temperature of each supply pipe from remaining the same, and the temperature of each supply pipe should be the same so that the droplet passing through at least one of the supply pipes or a vapor precursor or medium It is also a significant advantage of the present invention to form uniform thin films on the large area SUB2 by uniformizing the properties of the products.

At least one of the supply pipes PI1 may individually set the flow rate of the first precursor stream SP1 flowing therein. To this end, the internal cross sectional area of the supply pipes may be designed differently for each supply pipe. For example, the droplet flow rate in the supply pipe having a small internal cross-sectional area is larger than the droplet flow rate in the supply pipe having a large internal cross-sectional area. In another embodiment, a gate valve is provided in each supply pipe so that even if the internal cross-sectional areas of at least one of the supply pipes are equal to each other, the droplets delivered to each supply pipe can be turned on or off, The flow rate may also be controlled.

Although not shown, the in-line spray pyrolysis thin film forming apparatus 1000 may further include a first carrier gas supply unit coupled to the first raw material supply unit PP1 of the first nozzle unit 300A_1. The first carrier gas supply unit may have a valve system and a mass flow controller (MFC) that controls the supply flow rate of the carrier gas. The carrier gas supplied from the first carrier gas supply unit may include a first nozzle unit 300A_1 to the first deposition area DA1 of the reaction chamber CH and the carrier gas serves to push the first precursor to the reaction chamber CH and at least one of the supply pipes The first precursor stream SP1 is adsorbed on the inner wall of the PI1 or the inner wall of the slit SL1 to prevent it from becoming a dust or a contamination source.

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.

The slit SL1 may have an opening that crosses the output end of the supply pipes PI1 of the first supply part PP1. The slit may be a single opening or may comprise a plurality of slit-shaped openings.

In one embodiment, the first precursor stream SP1 provided at the first raw material supply part PP1 and transferred to at least one of the supply pipes PI1 may be provided to the object SUB2 via the slit SL1 have. A slit (SL1) of the first nozzle unit (300A_1) may have a first branch square (Θ ₁₎ relative to the direction perpendicular to the transport direction (A) of the workpiece (SUB2).

The first precursor stream SP1 provided from the slit SL1 of the first nozzle unit 300A_1 may be injected in a direction opposite to the conveying direction A of the subject SUB2. For example, the first spray angle? ₁ may be larger than 0 ° and less than 90 ° with respect to the vertical direction of the conveying direction A of the subject SUB2.

In another embodiment, the slits (SL1) of the first nozzle unit (300A_1) may have a first branch square (Θ ₁₎ relative to the direction perpendicular to the transport direction (A) of the workpiece (SUB2). A mixed stream in which the first precursor stream SP1 provided in the first raw material supply portion PP1 and the second precursor stream SP2 provided in the second raw material supply portion PP2 are mixed can be injected from the slit SL1.

The mixed stream may be provided in a direction opposite to the conveying direction A of the subject SUB2. For example, the first spray angle? ₁ may be larger than 0 ° and less than 90 ° with respect to the vertical direction of the conveying direction A of the subject SUB2.

It is preferable to form a uniform fine pattern on the workpiece SUB3 before the workpiece SUB2 deposited from the first nozzle portion 300A_1 is transferred to the workpiece SUB4 to be deposited from the second nozzle portion 300A_2 A film formation transfer step to form reaction conditions may be performed (S30).

 The object to be processed SUB2 in which the first precursor stream SP1 is sprayed and deposited is transferred in one direction A to define a film formation transfer area TA1 in which the film formation transfer step S30 of the object SUB3 is performed . The film deposition transfer area TA1 may be defined as a region between the first deposition area DA1 and the second deposition area DA2. In one embodiment, the temperature of the film formation transfer area TA1 may be higher than 200 DEG C and less than 600 DEG C. [

In addition, the film formation transfer area TA1 can be defined as a space between the first nozzle part 300A_1 and the second nozzle part 300A_2 of the reaction chamber CH. In one embodiment, the subject SUB2 may be transferred in one direction (A) to transfer the subject SUB3 to the film forming transfer area TA1.

 In one embodiment, the first precursor stream SP1 and the second precursor stream SP2 may not be provided on the subject SUB3 of the film forming transfer area TA1. For example, aging or annealing may be performed on the workpiece SUB3 of the film forming transfer area TA1 where the first precursor stream SP1 or the second precursor stream SP2 is not provided.

The aging or annealing can stabilize the reaction of the deposition deposited on the subject SUB3, or crystallize or grow the first layer formed in the first deposition area, for example, the generated nuclei, or to grow the grain in the thin film have. In addition, the object to be processed SUB3 of the film forming transfer area TA1 can relieve the stress accumulated in the thin film deposited in the first nozzle unit 300A_1 to prevent cracking of the thin film as a final product.

 In addition, since the substrate passes through the film formation transfer area TA1 defined between the first nozzle part 300A_1 and the second nozzle part 300A_2 to selectively transfer the properties of the thin film to form a uniform fine pattern on the substrate Reaction conditions can be formed.

The subject SUB4 transferred in the one direction A undergoes a second deposition step S40 in the second deposition area DA2 defined by the second nozzle part 300A_2. The second nozzle unit 300A_2 may be disposed behind the first nozzle unit 300A_1. The second nozzle unit 300A_2 ejects the second precursor stream PS2 onto the subject SUB4. The second nozzle unit 300A_2 may be coupled to at least one supply pipe PI2 for receiving the second precursor from the second material supply unit PP2 that generates and supplies the second precursor.

In one embodiment, the second nozzle portion 300A_2 for providing the second precursor stream PS2 comprises a mixing portion for uniform mixing of the carrier gas with the second precursor delivered from the second feedstock PP2 And a spray hole or slit SL2 for spraying a uniformly mixed second precursor gas. In FIG. 2B, it is exemplified that the first nozzle unit 300A_1 and the second nozzle unit 300A_2 have a common mixing unit MP so as to share the mixing unit.

The second nozzle unit 300A_2 can provide the second precursor stream PS2 in the forward direction with respect to the transport direction A of the workpiece SUB4. To this end, in one embodiment, the ejection holes or slits SL2 of the second nozzle unit 300A_2 may be provided in a forward direction with respect to the conveying direction A of the subject SUB4.

In one embodiment, the second precursor stream SP2 provided from the second nozzle portion 300A_2 is provided on the subject SUB4 to which the subject SUB3 is transferred in the first direction A to form a second precursor stream SP2 on the subject SUB4 The second layer may be deposited (S40). In one embodiment, a second deposition area DA2 of the reaction chamber CH that provides a second precursor stream PS2 to the subject SUB4 may be defined. In one embodiment, the temperature of the second deposition area DA2 may be higher than 200 [deg.] C and less than 400 [deg.] C.

The second precursor stream (PS2) comprises a second precursor or an intermediate product derived from the second precursor, wherein the second precursor is dissolved or dispersed in a small volume of solvent, an aerosol, or the solvent is vaporized . In one embodiment, the second precursor stream (PS2) may be for forming F-doped Tin Oxide (FTO). In this case, the second precursor is a chloride of tin as a tin precursor _{(SnCl 4 · 5H 2 O)} , (C 4 H 9) 2 Sn (CH 3 COO) 2, (CH 3) SnCl 3, (CH 3 ) ₂ SnCl ₂ , (CH ₃ ) ₃ SnCl ₁ or (C ₄ H ₉ ) ₃ SnH may be used and other precursors such as ((C ₄ H ₉ ) ₃ SnCl, (C ₄ H ₉ ) ₂ SnCl ₂ , or (C ₄ H ₉ ) SnCl ₃ ) may be used. Also, monobutyltin chloride, dibutyltin chloride or tributyltin chloride may be used as the tin precursor. These are illustrative, and the second precursor may comprise other tin-containing compounds as precursors of tin. Also, the second precursor may be a fluorine-containing compound such as ammonium fluoride (NH ₄ F), CF ₃ Br, CF ₂ Cl ₂ , CH ₃ CClF ₂ , CF ₃ COOH, or CH ₃ CHF ₂ as a fluorine precursor And the present invention is not limited thereto. In one embodiment, the solvent may comprise distilled water or alcohol, and the present invention is not limited thereto.

The second raw material supply portion PP2 may be provided with a starting solution containing a suitable starting compound and an energy source (not shown) for forming droplets from the surface or interface 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.

At least one of the supply pipes PI2 may be a flow path for transferring the second raw material supply pipe PP2 from the second raw material supply pipe PP2 to the second deposition area DA2 of the reaction chamber CH. In one embodiment, the second precursor provided from the second feedstock PP2 may be delivered via at least one feed pipes PI2 to provide a second precursor stream SP2 from the slit SL2.

If the second nozzle unit 300A_2 includes a single supply pipe, the thin film should be formed while moving the second nozzle unit 300A_2 evenly on the surface of the object to be coated on a large area of the object to be processed. In this case, in the region where the return path takes place during the movement path of the single feed pipe, the time for which the nozzles of the single feed pipe remain is increased so that the thickness of the coated thin film is smaller than the thickness of the thin film formed in the region where the single feed pipe simply passes. It can be big. However, according to the embodiment of the present invention, by arranging the single supply pipes side by side and expanding a plurality of them, it is possible to form a thin film having a uniform thickness on the large-area workpiece, It is possible to implement a continuous pattern without any dust.

At least one of the supply pipes PI2 may be formed of a metal conduit or a quartz conduit such as stainless steel having suitable heat resistance so as to be externally heated. In some embodiments, the inner surface of at least one of the supply pipes PI2 may be coated with a Teflon coating or a water repellent coating to prevent adhesion, in order to improve chemical resistance and corrosion resistance. Heating of the supply pipes PI2 may be performed by resistive heating in which a resistance wire is wrapped around the outside of the conduit or radiant heating such as a halogen lamp. Although not shown, the supply pipes PI2 may be installed in a separate housing for isolation from the outside.

Preferably, the at least one supply pipes PI2 may have a suitable temperature control system for individually adjusting the temperature of the inner second precursor stream SP2 for each supply pipe. In this case, a resistance heating method in which the resistance wire is wrapped around the outside of each supply pipe and the amount of electric power to be supplied can be individually adjusted for each flow channel may be advantageous. However, it should be understood that this individual adjustment does not preclude the temperature of each supply pipe from remaining the same, and the temperature of each supply pipe should be the same so that the droplet passing through at least one of the supply pipes or a vapor precursor or medium It is also a significant advantage of the present invention to form a homogeneous thin film on the large-area subject SUB4 by making the properties of the products uniform.

At least one of the supply pipes PI2 may separately set the flow rate of the second precursor stream SP2 flowing therein. To this end, the internal cross sectional area of the supply pipes may be designed differently for each supply pipe. For example, the droplet flow rate in the supply pipe having a small internal cross-sectional area is larger than the droplet flow rate in the supply pipe having a large internal cross-sectional area. In another embodiment, a gate valve is provided in each supply pipe so that even if the internal cross-sectional areas of at least one of the supply pipes are equal to each other, the droplets delivered to each supply pipe can be turned on or off, The flow rate may also be controlled.

Although not shown, the in-line spray pyrolysis thin film forming apparatus 1000 may further include a second carrier gas supply unit coupled to the second raw material supply unit PP2 of the second nozzle unit 300A_2. The second carrier gas supply unit may have a valve system and a mass flow controller (MFC) that controls the supply flow rate of the carrier gas. The carrier gas supplied from the second carrier gas supply unit may include a second nozzle unit 300A_2 to the second deposition area DA2 of the reaction chamber CH and the carrier gas serves to push the second precursor into the reaction chamber CH and at least one of the supply pipes The second precursor stream SP2 is adsorbed to the inner wall of the first precursor stream PI2 or the inner wall of the slit SL2 to prevent the second precursor stream SP2 from becoming a dust or a contamination source.

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.

The slit SL2 may have an opening that traverses the output end of the supply pipes PI2 of the second supply part PP2. The slit may be a single opening or may comprise a plurality of slit-shaped openings.

In one embodiment, a second precursor stream SP2 provided at the second feedstock PP2 and transferred to at least one feedstock PI2 may be provided to the subject SUB4 via the slit SL2 have. A slit (SL2) of the second nozzle part (300A_2) may have a second branch square ₍₂ Θ) relative to the direction perpendicular to the transport direction (A) of the workpiece (SUB2).

The second precursor stream SP2 provided from the slit SL2 of the second nozzle unit 300A_2 can be injected in the forward direction of the conveying direction A of the subject SUB4. For example, the second spray angle? ₂ may be larger than 0 ° and less than 90 ° with respect to the vertical direction of the conveying direction A of the subject SUB4.

In another embodiment, the second slit (SL1) of the nozzle portion (300A_2) may have a second branch square ₍₂ Θ) relative to the direction perpendicular to the transport direction (A) of the workpiece (SUB2). The mixed stream in which the first precursor stream SP1 provided in the first raw material supply portion PP1 and the second precursor stream SP2 provided in the second raw material supply portion PP2 are mixed can be injected from the slit SL2.

The mixed stream may be provided in the forward direction of the conveying direction A of the subject SUB4. For example, the second spray angle? ₂ may be larger than 0 ° and less than 90 ° with respect to the vertical direction of the conveying direction A of the subject SUB4.

In one embodiment, the first precursor stream SP1 and the second precursor stream SP2 may comprise the same material. Therefore, the first precursor stream SP1 provided from the first nozzle portion 300A_1 and the second precursor stream SP2 provided from the second nozzle portion 300A_2 include a precursor having the same property, (SP2) formed from a first precursor stream (SP2) formed from a first precursor stream (SP1) on a substrate and having the same properties as the first layer and having physical characteristics such as thickness and shape of a pattern A layer may be coated over the first layer.

In another embodiment, the first precursor stream (SP1) and the second precursor stream (SP2) may comprise different precursors. The first precursor stream SP1 provided from the first nozzle portion 300A_1 and the second precursor stream SP2 provided from the second nozzle portion 300A_2 have different properties so that the first precursor stream SP1 SP1 may be coated and a second layer formed from the second precursor stream SP2 may be coated over the first layer to form a dual thin film structure on the substrate.

In one embodiment, the first jetting angle? ₁ and the second jetting angle? ₂ can be symmetrically adjusted with respect to the vertical direction of the substrate. The width of the film-forming transition regions (TA1) is a target object relative to the direction perpendicular to the transport direction (A) of (SUB3) first branch square (Θ ₁₎ and a can be proportional to the sum of the sizes of two minutes square (Θ ₂₎ have.

Thereafter, the subject SUB4 can be transferred in one direction (A) for movement to the next exhaust area EA2 or the post-treatment area CA. In one embodiment, the apparatus 1000 for forming an in-line spray pyrolysis thin film may be provided with a shutter or an air curtain separately for sealing and opening / closing between reaction chambers CH. For example, a shutter or an air curtain may be installed between the second nozzle part 300A_2 and the second exhaust part 400. [ Further, a shutter or an air curtain may be installed between the second exhaust part 400 and the post-processing part 500.

In the apparatus 1000 for forming an in-line spray pyrolysis thin film, a second exhaust unit 400 may be installed at a rear end of the second nozzle unit 300A_2. The second exhaust part 400 of the in-line spray pyrolytic film forming apparatus 1000 can define the exhaust area EA2 in which the second evacuation step S45 is performed. In one embodiment, the second exhaust part 400 can be disposed in front of the post-processing part 500 based on the conveying direction A of the substrate.

Also, in one embodiment, while the second deposition step S40 is performed by the second nozzle part 300A_2, the second exhaust part 200 may perform the deposition transition step S30 or the second deposition step S40, A by-product, such as a reactant gas, a carrier gas, or an unreacted (or unreacted) gas that is used or formed at step S45.

In another embodiment, before the subject SUB4 on the support device CB undergoes a second deposition step S40 by the second nozzle portion 300A_2, a film deposition transition region TA1) or air or contaminants in the second deposition area DA2 may be discharged first through the second exhaust part 400. [

The subject SUB5 having undergone the second evacuation step S45 can be transported in the one direction A for movement to the post-treatment area CA. In one embodiment, the post-processing unit 500 may be installed at the rear end of the second exhaust unit 400 in the apparatus 1000 for forming an in-line spray pyrolysis thin film. The post-processing unit 500 of the in-line spray pyrolytic film forming apparatus 1000 may define a post-processing area CA in which the post-processing step S50 is performed. In one embodiment, the post-processing unit 500 may be installed at the end or outlet of the reaction chamber CH of the in-line spray pyrolytic thin film forming apparatus 1000 with reference to the transfer direction A of the substrate.

The post-processing unit 500 may coat a protective layer on the subject SUB5 to cool the surface of the subject SUB5 or protect the subject SUB5. The surface of the subject SUB5 can be quenched or cooled using a cooling device. The cooling device may be a functional cooling device that changes the physical properties of the surface of the subject SUB5. Also, an air cooling type, water cooling type or semiconductor cooling type cooling means may be used as the cooling device. In another embodiment, the subject SUB5 may be naturally cooled without using a cooling device.

In one embodiment, the apparatus 1000 for forming an in-line spray pyrolysis thin film may be provided with a shutter or an air curtain for sealing and opening / closing between reaction chambers CH. For example, a shutter or an air curtain may be installed between the post-processing unit 500 and the outlet of the in-line spray pyrolytic film forming apparatus 1000.

Thereafter, the subject SUB5 is transferred in one direction (A) and discharged from the inline spray pyrolysis thin film forming apparatus 1000 to form a uniform thin film on the substrate. (S60)

The apparatus for forming an in-line spray pyrolysis thin film according to an embodiment of the present invention includes a first nozzle unit for providing a precursor stream in a reverse direction to a transport direction of a substrate, and a second nozzle unit disposed at a rear side of the first nozzle unit, And a second nozzle portion for providing a precursor stream in a forward direction with respect to the transport direction of the substrate.

A film formation transition region in which the precursor stream is not provided between the first nozzle portion and the second nozzle portion is defined. The substrate provided with the precursor stream from the first nozzle portion can be annealed to the substrate in the deposition transition region by not receiving the precursor stream in the deposition transition region.

The annealing may stabilize the reaction of the film deposited on the substrate, nuclei in the film may be crystallized, or nuclei in the film may be grown. Further, in the film-forming transfer region, the substrate is released from the stress of the film deposited on the first nozzle portion, thereby preventing cracking of the film as the final product. Therefore, a reaction condition for forming a uniform fine pattern on the substrate passing through the deposition transition region defined between the first nozzle portion and the second nozzle portion can be formed.

In the apparatus for forming an in-line spray pyrolysis thin film according to an embodiment of the present invention, the first precursor stream supplied from the first nozzle unit and the second precursor stream supplied from the second nozzle unit have different properties, A first layer formed from the precursor stream is coated and a second layer formed from the second precursor stream is coated over the first layer to form a dual thin film structure on the substrate.

The method of forming an in-line spray pyrolysis thin film according to an embodiment of the present invention includes a deposition transition region between a first deposition region where a first precursor stream is deposited and a second deposition region where a second precursor stream is deposited. Also, the first precursor stream and the second precursor stream may be provided from a first nozzle portion or a second nozzle portion having a spray angle with respect to the vertical direction of the substrate.

Also, the spray angle of the first nozzle portion or the second nozzle portion providing the first precursor stream or the second precursor stream may be symmetrically adjusted with respect to the vertical direction of the substrate. Therefore, the film formation transfer area can be defined by the spray angle.

According to the embodiment of the present invention, in the apparatus for forming an in-line spray pyrolysis thin film or the method for forming an in-line spray pyrolysis thin film, the first precursor stream supplied from the first nozzle portion and the second precursor stream supplied from the second nozzle portion have the same property By including a precursor, it is formed from a first layer and a second precursor stream formed from a first precursor stream on a substrate in one in-line process, the properties being the same as the first layer, and being physically different A second layer having properties can be coated.

1 is a flowchart illustrating a method of forming an in-line spray pyrolysis thin film according to an embodiment of the present invention. FIG. 3A is a cross-sectional view showing an apparatus 1100 for forming an in-line spray pyrolysis thin film according to another embodiment of the present invention. 3B is a perspective view of a nozzle portion of the in-spray pyrolytic film forming apparatus 1100 of FIG. 3A. The apparatus 1200 for forming an in-line spray pyrolysis thin film according to an embodiment of the present invention can be used in the method for forming an in-line spray pyrolysis thin film according to the embodiment of the present invention shown in Fig.

The in-line spray pyrolytic film forming apparatus 1100 shown in FIG. 3A is identical to the in-line spray pyrolytic film forming apparatus 1000 shown in FIG. 2A except for the first nozzle unit 300B_1 and the second nozzle unit 300B_2 A detailed description thereof will be omitted.

The in-line spray pyrolysis thin film forming apparatus 1100 may include a support apparatus CB installed in the reaction chamber CH, a first nozzle unit 300B_1 and a second nozzle unit 300B_2. 3A illustrates a dual nozzle structure including a first nozzle unit 300A_1 and a second nozzle unit 300B_2 spaced from the first nozzle unit 300B_1. In another embodiment, the inline spray pyrolytic film forming apparatus 1100 May have three or more nozzle portions. Reference numeral 100, 200, 400, and 500 illustrate a pretreatment unit, a first exhaust unit, a second exhaust unit, and a post-treatment unit, respectively, and the in-line spray pyrolytic film forming apparatus 1100 of the present invention further includes at least one .

In one embodiment, the reaction chamber CH is divided into a pretreatment zone PA, an exhaust zone EA1, a first deposition zone DA1, a film deposition transfer zone TA2, a second deposition zone DA2, The area EA2 and the post-processing area CA. The support device CB of the in-line spray pyrolysis thin film forming apparatus 1100 includes a transfer system such as a conveyor belt or a roller device capable of transferring the substrate while coating the thin film on the surface. In one embodiment, the support apparatus CB supports the substrate and transports the substrate in one direction (A) so that the substrate is subjected to the processing steps PA, exhaust area EA1, first deposition area DA1, The film deposition transfer area TA2, the second deposition area DA2, the exhaust area EA2, and the post-treatment area CA.

Referring to FIG. 3B together with FIG. 1, the object to be processed SUB2 transferred in one direction A is subjected to a first deposition step S20 in a first deposition area DA1 defined by the first nozzle part 300B_1, ≪ / RTI > The first nozzle unit 300B_1 ejects the first precursor stream PS1 onto the subject SUB2. The first nozzle unit 300B_1 may be coupled to at least one supply pipe PI1 for transferring the first precursor from the first material supply unit PP1 that generates and supplies the first precursor.

In one embodiment, the first nozzle portion 300B_1 for providing the first precursor stream PS1 includes a first precursor body 300B_1, a first precursor body PP1, And a jet hole or slit SL1 for jetting gas. 3B illustrates a structure in which the first nozzle unit 300B_1 and the second nozzle unit 300B_2 to be described later are spaced apart from each other at a predetermined interval and installed in the reaction chamber CH.

The first nozzle portion 300B_1 can provide the first precursor stream PS1 in a direction opposite to the transport direction A of the workpiece SUB2. To this end, in one embodiment, the ejection holes or slits SL1 of the first nozzle unit 300B_1 may be provided in a direction opposite to the conveying direction A of the subject SUB2.

The second nozzle unit 300B_2 separated from the first nozzle unit 300B_1 may include a second raw material supply unit PP2 for generating and supplying a second precursor and at least one supply pipe PI2. The second precursor may comprise a homogeneous or heterogeneous material as the first precursor. The second nozzle unit 300B_2 is arranged in such a manner that the second nozzle unit 300B_2 for supplying the second precursor stream PS2 is supplied with the second precursor stream PP2 from the second raw material supply unit PP2, And a spray hole or slit SL2 for spraying the precursor gas. The second nozzle unit 300B_2 may be used in the second deposition step S40. This will be described in detail later.

 In one embodiment, a first precursor stream SP1 provided from a first nozzle portion 300B_1 is provided on a subject SUB2 to which a subject to be treated SUB1 is transferred in one direction A to form a first precursor stream SP1 on the subject SUB2 (S20). ≪ / RTI > In one embodiment, a first deposition area DA1 of a reaction chamber CH that provides a first precursor stream PS1 to a subject SUB2 may be defined. In one embodiment, the temperature of the first deposition area DA1 may be higher than 200 占 폚 and less than 400 占 폚.

The slit SL1 may have an opening that crosses the output end of the supply pipes PI1 of the first supply part PP1. The slit may be a single opening or may comprise a plurality of slit-shaped openings.

In one embodiment, the first precursor stream SP1 provided at the first raw material supply part PP1 and transferred to at least one of the supply pipes PI1 may be provided to the object SUB2 via the slit SL1 have. A slit (SL1) of the first nozzle unit (300B_1) may have a first branch square (Θ ₁₎ relative to the direction perpendicular to the transport direction (A) of the workpiece (SUB2).

The first precursor stream SP1 provided from the slit SL1 of the first nozzle unit 300B_1 may be injected in a direction opposite to the conveying direction A of the subject SUB2. For example, the first spray angle? ₁ may be larger than 0 ° and less than 90 ° with respect to the vertical direction of the conveying direction A of the subject SUB2.

It is necessary to form a uniform fine pattern on the subject SUB3 before the subject SUB2 deposited from the first nozzle portion 300B_1 is transferred to the subject SUB4 to be deposited from the second nozzle portion 300B_2 A film formation transfer step to form reaction conditions may be performed (S30).

The substrate SUB2 in which the first precursor stream SP1 is deposited and deposited is defined as a film formation transfer area TA2 in which a film formation transfer step S30 of the subject SUB3 is performed in the one direction A . The film formation transfer area TA2 can be defined as a region between the first deposition area DA1 and the second deposition area DA2. In one embodiment, the temperature of the film formation transfer area TA2 may be higher than 200 DEG C and less than 600 DEG C. [

In addition, the film formation transfer area TA2 can be defined as a space between the first nozzle part 300B_1 and the second nozzle part 300B_2 of the reaction chamber CH. In one embodiment, the subject SUB2 can be transferred in one direction A and the subject SUB3 can be transferred to the film formation transfer area TA2. In an embodiment, the first nozzle portion 300B_1 and the second nozzle portion 300B_2 may be spaced apart from each other by a width of the film formation transfer area TA2.

In one embodiment, the first precursor stream (SP1) or the second precursor stream (SP2) may not be provided on the subject SUB3 of the film forming transfer area TA2. For example, aging or annealing may be performed on the workpiece SUB3 of the film forming transfer area TA2 where the first precursor stream SP1 or the second precursor stream SP2 is not provided.

The aging or annealing can stabilize the reaction of the deposition deposited on the subject SUB3, or crystallize or grow the first layer formed in the first deposition area, for example, the generated nuclei, or to grow the grain in the thin film have. In addition, the object to be processed SUB3 of the film formation transfer area TA2 can relieve the stress accumulated in the thin film deposited by the first nozzle unit 300B_1 to prevent cracking of the thin film as a final product.

 In addition, since the substrate passes through the film formation transfer area TA2 defined between the first nozzle part 300B_1 and the second nozzle part 300B_2 to selectively transfer the properties of the thin film to form a uniform fine pattern on the substrate Reaction conditions can be formed.

The object to be processed SUB4 having the object to be processed SUB3 transferred in one direction A undergoes a second deposition step S40 in the second deposition area DA2 defined by the second nozzle part 300B_2. In one embodiment, the second nozzle portion 300B_2 may be disposed behind the first nozzle portion 300B_1. Also, the second nozzle unit 300B_2 may not be connected to the first nozzle unit 300B_1. The second nozzle unit 300B_2 ejects the second precursor stream PS2 onto the subject SUB4. The second nozzle unit 300B_2 may be coupled to at least one supply pipe PI2 for receiving the second precursor from the second material supply unit PP2 that generates and supplies the second precursor.

In one embodiment, the second nozzle portion 300B_2 for providing the second precursor stream PS2 includes a second precursor gas mixed with the second precursor delivered from the second feedstock PP2 and the carrier gas And a spray hole or slit SL2 for spraying. 3B illustrates a structure in which the first nozzle unit 300B_1 and the second nozzle unit 300B_2 are spaced apart from each other with a predetermined distance therebetween and installed in the reaction chamber CH.

The second nozzle unit 300B_2 can provide the second precursor stream PS2 in the forward direction with respect to the conveying direction A of the subject SUB4. To this end, in one embodiment, the ejection holes or slits SL2 of the second nozzle unit 300B_2 may be installed in a forward direction with respect to the conveying direction A of the subject SUB4.

In one embodiment, a second precursor stream SP2 provided from the second nozzle portion 300B_2 is provided on the subject SUB4 to which the subject SUB3 is transferred in one direction A to form a second precursor stream SP2 on the subject SUB4 The second layer may be deposited (S40). In one embodiment, a second deposition area DA2 of the reaction chamber CH that provides a second precursor stream PS2 to the subject SUB4 may be defined. In one embodiment, the temperature of the second deposition area DA2 may be higher than 200 [deg.] C and less than 400 [deg.] C.

The slit SL2 may have an opening that traverses the output end of the supply pipes PI2 of the second supply part PP2. The slit may be a single opening or may comprise a plurality of slit-shaped openings.

In one embodiment, a second precursor stream SP2 provided at the second feedstock PP2 and transferred to at least one feedstock PI2 may be provided to the subject SUB4 via the slit SL2 have. A slit (SL2) of the second nozzle part (300B_2) may have a second branch square ₍₂ Θ) relative to the direction perpendicular to the transport direction (A) of the workpiece (SUB2).

The second precursor stream SP2 provided from the slit SL2 of the second nozzle unit 300B_2 can be injected in the forward direction of the conveying direction A of the subject SUB4. For example, the second spray angle? ₂ may be larger than 0 ° and less than 90 ° with respect to the vertical direction of the conveying direction A of the subject SUB4.

In one embodiment, the first precursor stream SP1 and the second precursor stream SP2 may comprise the same material. Therefore, the first precursor stream SP1 provided from the first nozzle portion 300B_1 and the second precursor stream SP2 provided from the second nozzle portion 300B_2 include a precursor having the same property, (SP2) formed from a first precursor stream (SP2) formed from a first precursor stream (SP1) on a substrate and having the same properties as the first layer and having physical characteristics such as thickness and shape of a pattern A layer may be coated over the first layer.

In another embodiment, the first precursor stream (SP1) and the second precursor stream (SP2) may comprise different precursors. The first precursor stream SP1 provided from the first nozzle portion 300B_1 and the second precursor stream SP2 provided from the second nozzle portion 300B_2 have different properties so that the first precursor stream SP1 SP1 may be coated and a second layer formed from the second precursor stream SP2 may be coated over the first layer to form a dual thin film structure on the substrate.

In one embodiment, the first jetting angle? ₁ and the second jetting angle? ₂ can be symmetrically adjusted with respect to the vertical direction of the substrate. The width of the film deposition transfer area TA2 can be defined by the distance between the first nozzle part 300B_1 and the second nozzle part 300B_2. In addition, film formation based on the vertical direction of the transport direction (A) of the width of the object to be processed (SUB3) of the transition area (TA2) the first branch square (Θ ₁₎ and the second branch sum of the square (Θ ₂₎ the size and proportion can do.

According to an embodiment of the present invention, an apparatus for forming an in-line spray pyrolysis thin film is provided with a first nozzle portion for providing a precursor stream in a direction opposite to a transfer direction of a substrate, and a second nozzle portion And a second nozzle portion for providing a precursor stream in a forward direction with respect to the transport direction of the substrate. A film formation transition region in which the precursor stream is not provided between the first nozzle portion and the second nozzle portion is defined.

The substrate provided with the precursor stream from the first nozzle portion can be annealed to the substrate in the deposition transition region by not receiving the precursor stream in the deposition transition region.

The annealing may stabilize the reaction of the film deposited on the substrate, nuclei in the film may be crystallized, or nuclei in the film may be grown. Further, in the film-forming transfer region, the substrate is released from the stress of the film deposited on the first nozzle portion, thereby preventing cracking of the film as the final product. Therefore, the substrate passing through the deposition transition region defined between the first nozzle portion and the second nozzle portion can form a reaction condition for forming a uniform fine pattern.

In the apparatus for forming an in-line spray pyrolysis thin film according to an embodiment of the present invention, the first precursor stream supplied from the first nozzle unit and the second precursor stream supplied from the second nozzle unit have different properties, A first layer formed from the stream is coated and a second layer formed from the second precursor stream is coated over the first layer to form a dual thin film structure on the substrate.

The method of forming an in-line spray pyrolysis thin film according to an embodiment of the present invention includes a deposition transition region between a first deposition region where a first precursor stream is deposited and a second deposition region where a second precursor stream is deposited. Also, the first precursor stream and the second precursor stream may be provided from a first nozzle portion or a second nozzle portion having a spray angle with respect to the vertical direction of the substrate.

Also, the spray angle of the first nozzle portion or the second nozzle portion providing the first precursor stream or the second precursor stream may be symmetrically adjusted with respect to the vertical direction of the substrate. Therefore, the film formation transfer area can be defined by the spray angle.

According to the embodiment of the present invention, in the apparatus for forming an in-line spray pyrolysis thin film or the method for forming an in-line spray pyrolysis thin film, the first precursor stream supplied from the first nozzle portion and the second precursor stream supplied from the second nozzle portion have the same property By including a precursor, it is formed from a first layer and a second precursor stream formed from a first precursor stream on a substrate in one in-line process, the properties being the same as the first layer, and being physically different A second layer having properties can be coated.

1 is a flowchart illustrating a method of forming an in-line spray pyrolysis thin film according to an embodiment of the present invention. 4A is a cross-sectional view illustrating an apparatus for forming an in-line spray pyrolysis thin film 1200 according to another embodiment of the present invention. 4B is a perspective view of the nozzle portions of the in-spray pyrolytic film forming apparatus 1200 of FIG. 4A. The apparatus 1200 for forming an in-line spray pyrolysis thin film according to an embodiment of the present invention can be used in the method for forming an in-line spray pyrolysis thin film according to the embodiment of the present invention shown in Fig.

The in-line spray pyrolysis thin film forming apparatus 1200 shown in FIG. 4A is the same as the in-line spray pyrolytic film forming apparatus 1000 shown in FIG. 2A except for the first nozzle unit 300C_1 and the second nozzle unit 300C_2 A detailed description thereof will be omitted.

The inline spray pyrolysis thin film forming apparatus 1200 may include a supporting device CB installed in the reaction chamber CH and a first nozzle portion 300C_1 and a second nozzle portion 300C_2. In an embodiment, the inline spray pyrolysis thin film forming apparatus 1200 may further include a rotation unit CP between the first nozzle unit 300C_1 and the second nozzle unit 300C_2.

4A illustrates a dual nozzle structure consisting of a first nozzle portion 300C_1 and a second nozzle portion 300C_2, but in other embodiments, the in-line spray pyrolytic thin film forming apparatus 1200 may have three or more nozzle portions . Reference numeral 100, 200, 400, and 500 illustrate a pretreatment unit, a first exhaust unit, a second exhaust unit, and a post-treatment unit, respectively, and the in-line spray pyrolytic film formation apparatus 1200 of the present invention further includes at least one .

In one embodiment, the reaction chamber CH is divided into a pretreatment zone PA, an exhaust zone EA1, a first deposition zone DA1, a film deposition transfer zone TA3, a second deposition zone DA2, The area EA2 and the post-processing area CA. The support device CB of the in-line spray pyrolysis thin film forming apparatus 1200 includes a transfer system such as a conveyor belt or roller device capable of transferring the substrate while coating the thin film on the surface. In one embodiment, the support apparatus CB supports the substrate and transports the substrate in one direction (A) so that the substrate is subjected to the processing steps PA, exhaust area EA1, first deposition area DA1, The film deposition transfer area TA3, the second deposition area DA2, the exhaust area EA2, and the post-treatment area CA.

Referring to FIG. 4B together with FIG. 1, a subject SUB2 transferred in one direction A is subjected to a first deposition step S20 in a first deposition area DA1 defined by the first nozzle part 300C_1, ≪ / RTI > The first nozzle unit 300C_1 ejects the first precursor stream PS1 onto the subject SUB2. The first nozzle unit 300C_1 may be coupled to at least one supply pipe PI1 for transferring the first precursor from the first material supply unit PP1 that generates and supplies the first precursor.

In one embodiment, the first nozzle portion 300C_1 for providing the first precursor stream PS1 includes a mixing portion for uniform mixing of the first precursor delivered from the first feedstock PP1 and the carrier gas, And a spray hole or slit SL1 for spraying the uniformly mixed first precursor gas. In FIG. 4B, the first nozzle unit 300C_1 and the second nozzle unit 300C_2 to be described later share the mixing unit, and the mixing unit is rotated by the rotation unit CP to circulate the first precursor gas. The rotating part CP may comprise a cylindrical mixing vessel, which can be rotated in one direction to circulate the first precursor stream PS1 or the second precursor stream SP2. The rotation speed of the rotation unit may be adjusted by a separate control unit.

The first nozzle unit 300C_1 can provide the first precursor stream PS1 in a reverse direction with respect to the transport direction A of the workpiece SUB2. To this end, in one embodiment, the injection hole or slit SL1 of the first nozzle unit 300C_1 may be provided in a direction opposite to the conveying direction A of the subject SUB2.

In one embodiment, the first nozzle portion 300C_1 may be connected to the rotation portion CP. The rotation part CP can be rotated in one direction to have a centrifugal force. Accordingly, the first precursor stream PS1 or the second precursor stream PS2 supplied from the first nozzle portion 300C_1 can be uniformly circulated or the reaction between them can be activated.

Similar to the first nozzle unit 300C_1, the second nozzle unit 300C_2 may include a second raw material supply unit PP2 for generating and supplying a second precursor and at least one supply pipe PI2. The second precursor may comprise a homogeneous or heterogeneous material as the first precursor. The second nozzle portion 300C_2 is provided for the uniform mixing of the carrier gas with the second precursor delivered from the second feedstock PP2 for providing the second precursor stream PS2. And a spray hole or slit SL2 for spraying a second precursor gas uniformly mixed with the mixing portion. The second nozzle unit 300C_2 may be used in the second deposition step S40. This will be described in detail later.

In one embodiment, a first precursor stream SP1 provided from a first nozzle portion 300C_1 is provided on a subject SUB2 to which a subject to be treated SUB1 is transferred in one direction A to form a first precursor stream SP1 on the subject SUB2 (S20). ≪ / RTI > In one embodiment, a first deposition area DA1 of a reaction chamber CH that provides a first precursor stream PS1 to a subject SUB2 may be defined. In one embodiment, the temperature of the first deposition area DA1 may be higher than 200 占 폚 and less than 400 占 폚.

The slit SL1 may have an opening that crosses the output end of the supply pipes PI1 of the first supply part PP1. The slit may be a single opening or may comprise a plurality of slit-shaped openings.

In one embodiment, the first precursor stream SP1 provided at the first raw material supply part PP1 and transferred to at least one of the supply pipes PI1 may be provided to the object SUB2 via the slit SL1 have. A slit (SL1) of the first nozzle unit (300C_1) may have a first branch square (Θ ₁₎ relative to the direction perpendicular to the transport direction (A) of the workpiece (SUB2).

The first precursor stream SP1 provided from the slit SL1 of the first nozzle unit 300C_1 can be injected in a direction opposite to the conveying direction A of the subject SUB2. For example, the first spray angle? ₁ may be larger than 0 ° and less than 90 ° with respect to the vertical direction of the conveying direction A of the subject SUB2.

In another embodiment, the slits (SL1) of the first nozzle unit (300C_1) may have a first branch square (Θ ₁₎ relative to the direction perpendicular to the transport direction (A) of the workpiece (SUB2). A mixed stream in which the first precursor stream SP1 provided in the first raw material supply portion PP1 and the second precursor stream SP2 provided in the second raw material supply portion PP2 are mixed can be injected from the slit SL1.

The mixed stream may be provided in a direction opposite to the conveying direction A of the subject SUB2. For example, the first spray angle? ₁ may be larger than 0 ° and less than 90 ° with respect to the vertical direction of the conveying direction A of the subject SUB2.

It is preferable to form a uniform fine pattern on the workpiece SUB3 before the workpiece SUB2 deposited from the first nozzle portion 300C_1 is transferred to the workpiece SUB4 to be deposited from the second nozzle portion 300C_2 A film formation transfer step to form reaction conditions may be performed (S30).

The object to be processed SUB2 in which the first precursor stream SP1 is sprayed and deposited is transferred in one direction A to define a film formation transfer area TA3 in which the film formation transfer step S30 of the object SUB3 is performed . The film formation transfer area TA3 may be defined as a region between the first deposition area DA1 and the second deposition area DA2. In one embodiment, the temperature of the film formation transfer area TA3 may be higher than 200 DEG C and less than 600 DEG C.

Further, the film formation transfer area TA3 may be defined as a space between the first nozzle part 300C_1 and the second nozzle part 300C_2 of the reaction chamber CH. In one embodiment, the subject SUB2 can be transferred in one direction A and the subject SUB3 can be transferred to the film formation transfer area TA3.

In one embodiment, the first precursor stream SP1 and the second precursor stream SP2 may not be provided on the subject SUB3 of the film forming transfer area TA3. For example, aging or annealing may be performed on the workpiece SUB3 of the film forming transfer area TA3 where the first precursor stream SP1 or the second precursor stream SP2 is not provided.

The aging or annealing can stabilize the reaction of the deposition deposited on the subject SUB3, or crystallize or grow the first layer formed in the first deposition area, for example, the generated nuclei, or to grow the grain in the thin film have. In addition, the object to be processed SUB3 of the film formation transfer area TA3 can relieve the accumulated stress in the thin film deposited in the first nozzle part 300C_1 to prevent cracking of the thin film as a final product.

 In addition, since the substrate passes through the film forming transfer area TA3 defined between the first nozzle part 300C_1 and the second nozzle part 300C_2 to selectively transfer the properties of the thin film to form a uniform fine pattern on the substrate Reaction conditions can be formed.

The subject SUB4 transferred in the one direction A undergoes a second deposition step S40 in the second deposition area DA2 defined by the second nozzle part 300C_2. The second nozzle unit 300C_2 may be disposed behind the first nozzle unit 300C_1. The second nozzle unit 300C_2 may be symmetrically connected to the first nozzle unit 300C_1 around the rotation unit CP.

The second nozzle unit 300C_2 ejects the second precursor stream PS2 onto the subject SUB4. The second nozzle unit 300C_2 may be coupled to at least one supply pipe PI2 for receiving the second precursor from the second material supply unit PP2 that generates and supplies the second precursor.

In one embodiment, the second nozzle portion 300C_2 for providing the second precursor stream PS2 comprises a mixing portion for uniform mixing of the carrier gas with the second precursor delivered from the second feedstock PP2 And a spray hole or slit SL2 for spraying a uniformly mixed second precursor gas. In FIG. 4B, the first nozzle unit 300C_1 and the second nozzle unit 300C_2 share the mixing unit, and the mixing unit is rotated by the rotation unit CP to circulate the second precursor gas.

The second nozzle unit 300C_2 can provide the second precursor stream PS2 in the forward direction with respect to the transport direction A of the workpiece SUB4. To this end, in one embodiment, the injection hole or slit SL2 of the second nozzle unit 300C_2 may be installed in a forward direction with respect to the conveying direction A of the subject SUB4.

In one embodiment, the second nozzle portion 300C_2 may be connected to the rotation portion CP. The rotation part CP can be rotated in one direction to have a centrifugal force. Therefore, the first precursor stream PS1 or the second precursor stream PS2 supplied from the second nozzle portion 300C_2 can be uniformly circulated or the reaction between them can be activated.

In one embodiment, a second precursor stream SP2 provided from the second nozzle portion 300C_2 is provided on the subject SUB4 to which the subject SUB3 is transferred in one direction A to form a second precursor stream SP2 on the subject SUB4 The second layer may be deposited (S40). In one embodiment, a second deposition area DA2 of the reaction chamber CH that provides a second precursor stream PS2 to the subject SUB4 may be defined. In one embodiment, the temperature of the second deposition area DA2 may be higher than 200 [deg.] C and less than 400 [deg.] C.

The slit SL2 may have an opening that traverses the output end of the supply pipes PI2 of the second supply part PP2. The slit may be a single opening or may comprise a plurality of slit-shaped openings.

In one embodiment, a second precursor stream SP2 provided at the second feedstock PP2 and transferred to at least one feedstock PI2 may be provided to the subject SUB4 via the slit SL2 have. A slit (SL2) of the second nozzle part (300C_2) may have a second branch square ₍₂ Θ) relative to the direction perpendicular to the transport direction (A) of the workpiece (SUB2).

The second precursor stream SP2 provided from the slit SL2 of the second nozzle unit 300C_2 can be injected in the forward direction of the conveying direction A of the subject SUB4. For example, the second spray angle? ₂ may be larger than 0 ° and less than 90 ° with respect to the vertical direction of the conveying direction A of the subject SUB4.

In other embodiments, slits (SL2) of the second nozzle part (200C_2) may have a second branch square ₍₂ Θ) relative to the direction perpendicular to the transport direction (A) of the workpiece (SUB2). The mixed stream in which the first precursor stream SP1 provided in the first raw material supply portion PP1 and the second precursor stream SP2 provided in the second raw material supply portion PP2 are mixed can be injected from the slit SL2.

The mixed stream may be provided in the forward direction of the conveying direction A of the subject SUB4. For example, the second spray angle? ₂ may be larger than 0 ° and less than 90 ° with respect to the vertical direction of the conveying direction A of the subject SUB4.

In one embodiment, the first precursor stream SP1 and the second precursor stream SP2 may comprise the same material. Accordingly, the first precursor stream SP1 provided from the first nozzle unit 300C_1 and the second precursor stream SP2 provided from the second nozzle unit 300C_2 include a precursor having the same property, (SP2) formed from a first precursor stream (SP2) formed from a first precursor stream (SP1) on a substrate and having the same properties as the first layer and having physical characteristics such as thickness and shape of a pattern A layer may be coated over the first layer.

In another embodiment, the first precursor stream (SP1) and the second precursor stream (SP2) may comprise different precursors. The first precursor stream SP1 provided from the first nozzle portion 300C_1 and the second precursor stream SP2 provided from the second nozzle portion 300C_2 have different properties so that the first precursor stream SP1 SP1 may be coated and a second layer formed from the second precursor stream SP2 may be coated over the first layer to form a dual thin film structure on the substrate.

In one embodiment, the first jetting angle? ₁ and the second jetting angle? ₂ can be symmetrically adjusted with respect to the vertical direction of the substrate. The width of the film formation transfer area TA3 may be proportional to the diameter of the rotation part CP. In addition, film formation based on the vertical direction of the transport direction (A) of the width of the object to be processed (SUB3) of the transition area (TA3) the first branch square (Θ ₁₎ and the second branch sum of the square (Θ ₂₎ the size and proportion can do.

In the apparatus for forming an in-line spray pyrolysis thin film according to an embodiment of the present invention, the first precursor stream supplied from the first nozzle unit and the second precursor stream supplied from the second nozzle unit have different properties, A first layer formed from the stream is coated and a second layer formed from the second precursor stream is coated over the first layer to form a dual thin film structure on the substrate.

The method of forming an in-line spray pyrolysis thin film according to an embodiment of the present invention includes a deposition transition region between a first deposition region where a first precursor stream is deposited and a second deposition region where a second precursor stream is deposited. Also, the first precursor stream and the second precursor stream may be provided from a first nozzle portion or a second nozzle portion having a spray angle with respect to the vertical direction of the substrate.

Also, the spray angle of the first nozzle portion or the second nozzle portion providing the first precursor stream or the second precursor stream may be symmetrically adjusted with respect to the vertical direction of the substrate. Therefore, the film formation transfer area can be defined by the spray angle.

According to the embodiment of the present invention, in the apparatus for forming an in-line spray pyrolysis thin film or the method for forming an in-line spray pyrolysis thin film, the first precursor stream supplied from the first nozzle portion and the second precursor stream supplied from the second nozzle portion have the same property By including a precursor, it is formed from a first layer and a second precursor stream formed from a first precursor stream on a substrate in one in-line process, the properties being the same as the first layer, and being physically different A second layer having properties can be coated.

In one embodiment, the ejecting directions of the first nozzle portion 300C_1 and the second nozzle portion 300C_2 with respect to the vertical direction of the substrate may be symmetrical. The injection angle of the first nozzle unit 300C_1 and the second nozzle unit 300C_2 with respect to the vertical direction of the substrate can be adjusted by the rotation unit CP. The slit SL1 of the first nozzle unit 300C_1 and the slit SL2 of the second nozzle unit 300C_2 with respect to the vertical direction of the substrate may be symmetrical with respect to the rotation unit CP.

In the apparatus for forming an in-line spray pyrolysis thin film according to an embodiment of the present invention, the first precursor stream supplied from the first nozzle unit and the second precursor stream supplied from the second nozzle unit have different properties, A first layer formed from the precursor stream is coated and a second layer formed from the second precursor stream is coated over the first layer to form a dual thin film structure on the substrate.

The method of forming an in-line spray pyrolysis thin film according to an embodiment of the present invention includes a deposition transition region between a first deposition region where a first precursor stream is deposited and a second deposition region where a second precursor stream is deposited. Also, the first precursor stream and the second precursor stream may be provided from a first nozzle portion or a second nozzle portion having a spray angle with respect to the vertical direction of the substrate.

Also, the spray angle of the first nozzle portion or the second nozzle portion providing the first precursor stream or the second precursor stream may be symmetrically adjusted with respect to the vertical direction of the substrate. Therefore, the film formation transfer area can be defined by the spray angle.

According to the embodiment of the present invention, in the apparatus for forming an in-line spray pyrolysis thin film or the method for forming an in-line spray pyrolysis thin film, the first precursor stream supplied from the first nozzle portion and the second precursor stream supplied from the second nozzle portion have the same property By including a precursor, it is formed from a first layer and a second precursor stream formed from a first precursor stream on a substrate in one in-line process, the properties being the same as the first layer, and being physically different A second layer having properties can be coated.

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 as defined in the appended claims. Will be apparent to those of ordinary skill in the art.

Claims (26)

A supporting device for supporting and transporting the substrate;
Has a reverse to the first service precursor stream, so as to define a first accumulation region first branch square (Θ ₁₎ on the basis of a direction perpendicular to the conveying direction with respect to the transport direction of the substrate, perpendicular to the transport direction A first nozzle unit including a slit arranged in a direction of the first nozzle;
And a second precursor stream is provided in a forward direction with respect to the transport direction of the substrate to define a second deposition area, wherein the second precursor stream is provided in a direction perpendicular to the transport direction as to have a second branch square (Θ ₂₎ symmetrical to the first branch square (Θ ₁₎ and a second nozzle part comprises a slit that is arranged in a direction perpendicular to the transport direction; And
Wherein the film deposition transition region is formed between the first deposition region and the second deposition region. The method according to claim 1,
Wherein the supporting device comprises a heater for heating the substrate. The method according to claim 1,
Wherein the film deposition transfer zone is free of the first precursor stream and the second precursor stream. The method according to claim 1,
Wherein a reaction condition for forming a uniform fine pattern on the substrate is formed in the film formation transfer area. 5. The method of claim 4,
Wherein the substrate is annealed, the stress is released to prevent cracking, or the nuclei are crystallized or nuclei are grown. The method according to claim 1,
A first exhaust unit disposed in front of the first nozzle unit with respect to a conveying direction of the substrate; And
And a second exhaust unit disposed behind the second nozzle unit with respect to a conveying direction of the substrate. The method according to claim 1,
Wherein the first precursor stream and the second precursor stream comprise the same precursor. The method according to claim 1,
Wherein the first precursor stream and the second precursor stream comprise different precursors. The method according to claim 1,
Wherein the spray angle of the first precursor stream and the second precursor stream is controlled. The method according to claim 1,
Wherein the spray angle of the first precursor stream and the second precursor stream is symmetrically adjusted with respect to the vertical direction of the substrate. The method according to claim 1,
It said first nozzle portion and a second chloride through the second nozzle part tin _{(SnCl 4 · 5H 2 0)} , ammonium fluoride (NH ₄ F) and the solvent is supplied to the mixed precursor solution, the fluorine-containing tin oxide film ( fluorine doped tin oxide). The method according to claim 1,
Wherein the temperature of the deposition transition zone is higher than 200 占 폚 and lower than 600 占 폚. Providing a substrate on a support device capable of transferring a substrate;
Wherein the substrate has a first spray angle (? ₁ ) as a reference in a direction perpendicular to a conveying direction of the substrate while the substrate is being conveyed, and the substrate is conveyed in a reverse direction with respect to a conveying direction of the substrate through a slit aligned in a vertical direction of the conveying direction A first deposition step of providing a first precursor stream to the first precursor;
Forming a reaction condition for forming a fine pattern from the first deposit formed in the first depositing step after the first depositing step;
And a second ejection angle (? ₂ ) symmetrical to the _first ejection angle (? ₁ ) with respect to a vertical direction in the feeding direction during the transfer of the substrate after the film formation transfer step, And a second deposition step of providing a second precursor stream in a forward direction with respect to the transport direction of the substrate through the slit arranged in the vertical direction of the substrate. 14. The method of claim 13,
Wherein the first precursor stream and the second precursor stream are provided by a nozzle portion having at least one or more nozzles. 14. The method of claim 13,
Wherein the support device comprises a heater for heating the substrate. 14. The method of claim 13,
Wherein the deposition transition step does not provide a precursor stream for a predetermined time. 14. The method of claim 13,
Wherein the substrate is annealed, the stress is released to prevent cracking, crystallization of the generated nuclei, and nucleation are grown in the film formation transfer step. 14. The method of claim 13,
A first exhausting step of exhausting byproducts generated in the first depositing step; And
And a second evacuation step of evacuating the byproducts generated in the second deposition step. 14. The method of claim 13,
Wherein the first precursor stream and the second precursor stream comprise the same precursor. 14. The method of claim 13,
Wherein the first precursor stream and the second precursor stream comprise different precursors. 15. The method of claim 14,
Wherein the spray angle of the first precursor stream and the second precursor stream is controlled by the nozzle unit. 14. The method of claim 13,
Wherein the spray angle of the first precursor stream and the second precursor stream is symmetrically adjusted with respect to the vertical direction of the substrate. 14. The method of claim 13,
The first precursor or the second precursor stream stream is stannic chloride _{(SnCl 4 · 5H 2 0)} , ammonium fluoride (NH ₄ F) and in-line spray pyrolysis method for forming a thin film comprising a solvent. 14. The method of claim 13,
Wherein the temperature of the film deposition transfer step is performed at 200 to 600 占 폚. 14. The method of claim 13,
Further comprising: after the substrate is provided, surface-treating the substrate. 14. The method of claim 13,
Further comprising rapidly cooling and cooling the substrate. ≪ RTI ID = 0.0 > 11. < / RTI >

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