WO2016028012A1 - Precursor supplying device for forming thin film and thin film forming device comprising same - Google Patents

Abstract

The present invention relates to a precursor supplying device for forming a thin film, a thin film forming device comprising same, and a thin film forming method using same. The precursor supplying device, according to one embodiment of the present invention, comprises: a raw material storage part for storing a liquid raw material; a droplet supply part coupling to the raw material storage part for discharging the liquid raw material in the shape of droplets; and a precursor vaporization part comprising a chamber wall, a droplet inlet, a heating part, a carrier gas inlet, and a precursor outlet, the chamber wall limiting a vaporization space, the droplet inlet being formed on a first side part of the chamber wall for having droplets pass from the droplet supply part to the vaporization space, the heating part being coupled to the vaporization space for vaporizing the droplets in the vaporization space, thereby forming a vapor precursor in the vaporization space, the carrier gas inlet being formed on a second side part of the chamber wall for introducing carrier gas inside the vaporization space, and the precursor outlet being formed on a third side part of the chamber wall for outputting, to a reaction chamber, the vapor precursor mixed with the carrier gas.

Description

Precursor supply apparatus for forming a thin film and a thin film forming apparatus including the same

The present invention relates to a vapor deposition technique, and more particularly, to a precursor supply apparatus for forming a thin film, and a thin film forming apparatus including the same.

BACKGROUND ART In a solar cell, a liquid crystal display, an organic light emitting display (OLED), or a plasma display device, a substrate having a transparent conductive film formed on a transparent substrate such as a glass substrate as an insulator is widely used. As the transparent conductive film, a conductive metal oxide such as indium tin oxide (ITO), tin oxide, or fluorine-doped tin oxide (FTO) is typical. Among these oxides, transparent conductive films containing ITO as a main component have been widely applied to display devices for personal computers, televisions, and digital signage.

Recently, as an eco-friendly technology for carbon suppression policy and energy saving, there is an attempt to apply a transparent conductive film for resistance heating by direct electric energy instead of the conventional fossil fuel. For example, there is 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 for a plastic house, a livestock raising facility, or a food processing facility, or is used as a heat generating resistor for preventing condensation or freezing on window glass of a building, a car, or an aircraft. .

Among the above-mentioned applications, in the case of window glass, the FTO conductive film is attracting attention as a potent candidate material because it has not only high transparency but little resistance change up to 500 ° C., and also has excellent chemical resistance and abrasion resistance and is suitable for harsh external environments. have. The formation of the FTO conductive film is generally made by a vapor deposition method such as chemical vapor deposition (CVD), atomic layer deposition (ALD) or organic vapor deposition (OVPD or condensation coating).

However, since the substrate such as window glass has various sizes or large areas, and has various shapes such as a plate or a curved surface according to its application, it is difficult to implement the designed characteristics by the above-described vapor deposition method. . In addition, a large amount of raw materials are required to deposit a conductive film on a large-area or various shapes of substrates, and as a result, manufacturing costs increase due to unreacted and wasted raw materials.

The technical problem to be solved by the present invention is to minimize the waste of raw materials for forming a thin film, and to form a thin film having uniform characteristics economically and easily on a target object having various areas and shapes, such as a glass window. It is to provide a precursor supply device for providing a precursor.

In addition, another technical problem to be solved by the present invention is to provide a thin film forming apparatus having a precursor supply device having the above-described advantages.

Precursor supply apparatus according to an embodiment of the present invention for solving the above technical problem, is coupled to the reaction chamber for forming a thin film on one surface of the workpiece, vapor phase precursor for forming the thin film with the reaction chamber A precursor supply device for supplying a, comprising: a raw material storage unit for storing a liquid raw material; A droplet supply unit coupled to the raw material storage unit and configured to discharge the liquid raw material in the form of droplets; And a chamber wall defining a vaporization space; A droplet inlet formed on the first side of the chamber wall, through which droplets pass from the droplet supply to the vaporization space; A heating unit coupled to the vaporization space to vaporize the droplets in the vaporization space to form a gaseous precursor in the vaporization space; A carrier gas inlet formed on the second side of the chamber wall for introducing carrier gas into the vaporization space; And a precursor vaporization portion formed on the third side of the chamber wall and including a precursor outlet for outputting the gaseous precursor mixed with the carrier gas to the reaction chamber.

In one embodiment, the droplet supply unit may include a droplet flow rate control unit for controlling at least one of the moving speed and the size of the droplet. In addition, the flow control unit may include any one or a combination of two or more of the flow control valve, the directional control valve, the piston, and the clamp.

Temperature control means for preventing condensation from being generated by condensation of droplets on the outer wall or inside of the droplet supply unit may be provided. In addition, a plurality of droplet supply units may be provided, and different types of raw materials may be supplied to each droplet supply unit.

In one embodiment, the droplet inlet is a hole, through which the droplet supply portion may extend and protrude into the vaporization space. The droplet inlet may be a droplet path or a nozzle coupled to the chamber wall to protrude into the vaporization space, and the droplet supply unit may be coupled to the droplet inlet.

The first side of the chamber wall to which the droplet supply unit is coupled may be an upper side of the chamber wall, and the droplet supply unit may extend vertically. The droplet supply portion or the droplet inlet has a tube shape and may have a constant, increased or decreased inner diameter in the extending direction.

The droplet supply unit or the droplet inlet may reduce or interrupt the flow rate of the liquid raw material supplied from the raw material storage unit by using the surface tension of the liquid raw materials to the end of the droplet supply unit or the droplet inlet. The droplets may be generated by a method in which the particles form a droplet. In addition, the droplet supply unit or the droplet inlet is a method for forcibly discharging the liquid raw material in the form of droplets through the piezoelectric element coupled to the droplet supply unit or the droplet inlet or an electrode capable of forming an electric field when the liquid raw material is ionic The droplets can be generated as The droplet supply unit or the droplet inlet may adjust the size of the droplets by adjusting the size of the inner diameter.

In one embodiment, the heating portion is in the form of a plate, a vessel, a tube having a through hole through which droplets can pass, a coil, a rod, a fullerine and a net, or a combination thereof. Can be. The heating unit may be in contact with the vaporization space or coupled to the outside of the chamber wall. In addition, the droplet inlet and the heating unit may be disposed to face each other.

The heating unit may include any one or a combination of two or more of a far infrared heating device, an infrared heating device, a microwave heating device, an induction heating device, a dielectric heating device and a resistance heating device. The opening of the precursor outlet may have a shape having a cross section gradually extended toward the reaction chamber.

According to an aspect of the present invention, there is provided a thin film forming apparatus comprising: a reaction chamber defining a space for forming a thin film on one surface of a workpiece; Support means for placing the object to be processed in the reaction chamber; And a precursor supply device coupled to the reaction chamber for spraying a gaseous precursor on one surface of the object, the precursor supply device comprising: a raw material storage unit for storing a liquid raw material; A droplet supply unit coupled to the raw material storage unit and configured to discharge the liquid raw material in the form of droplets; And a chamber wall defining a vaporization space; A droplet inlet formed on the first side of the chamber wall, through which droplets pass from the droplet supply to the vaporization space; A heating unit coupled to the vaporization space to vaporize the droplets in the vaporization space to form a gaseous precursor in the vaporization space; A carrier gas inlet formed on the second side of the chamber wall for introducing carrier gas into the vaporization space; And a precursor supply chamber formed on the third side of the chamber wall and including a precursor outlet for outputting the gaseous precursor mixed with the carrier gas to the reaction chamber.

In one embodiment, the support means may comprise any one or a combination of a non-contact structure by an electromagnet or a permanent magnet, and a mechanical electric motor using a contact structure to rotate the workpiece. In addition, the thin film forming apparatus may form the thin film by spray pyrolysis.

According to an embodiment of the present invention, by discharging the liquid raw material in the form of droplets capable of temperature, speed and size control, and forming a vapor phase precursor from the discharged droplets, various areas and A vapor phase precursor supply device capable of easily forming a thin film of uniform properties on a workpiece having a shape can be provided.

Further, according to an embodiment of the present invention, there is provided a thin film forming apparatus that can easily form a thin film of uniform characteristics using the precursor supply apparatus described above.

1A shows a precursor vaporization portion in accordance with one embodiment of the present invention.

1B shows a precursor supply apparatus according to an embodiment of the present invention.

2A is another embodiment of a precursor outlet in accordance with one embodiment of the present invention.

2B is another embodiment of a precursor outlet in accordance with one embodiment of the present invention.

3 illustrates a thin film forming apparatus according to an embodiment of the present invention.

4A is a perspective view of a thin film forming apparatus according to an embodiment of the present invention.

4B is a side view of a thin film forming apparatus according to an embodiment of the present invention.

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

The embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art, and the following examples can be modified in various other forms, and the scope of the present invention is It is not limited to an Example. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the inventive concept to those skilled in the art.

In addition, in the following drawings, the thickness or size of each layer is exaggerated for convenience and clarity of description, the same reference numerals in the drawings refer to the same elements. As used herein, the term “and / or” includes any and all combinations of one or more 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" may include the plural forms as well, unless the context clearly indicates otherwise. Also, as used herein, "comprise" and / or "comprising" specifies the presence of the mentioned shapes, numbers, steps, actions, members, elements and / or groups of these. It is not intended to exclude the presence or the addition of one or more other shapes, numbers, acts, members, elements and / or groups.

Although the terms first, second, etc. are used herein to describe various members, parts, regions, layers, and / or parts, these members, parts, regions, layers, and / or parts are defined by these terms. It is obvious that not. These terms are only used to distinguish one member, part, region, layer or portion from another region, layer or portion. Thus, the first member, part, region, layer or portion, which will be discussed below, may refer to the second member, component, region, layer or portion without departing from the teachings of the present invention.

The thin film forming apparatus according to the embodiment of the present invention, more specifically, the transparent conductive film forming apparatus may be based on spray pyrolysis deposition (SPD). The spray pyrolysis method involves spraying droplets containing a raw compound produced using a spraying means such as an atomizer, such that evaporation, high temperature reaction, pyrolysis of the solvent contained in the droplets while the droplets are transferred through the droplet delivery flow path. , Gas phase, collectively referred to herein, involving at least one or two or more steps of the reaction between the carrier gas and the precursor (eg, oxidation or reduction), the formation of clusters, and the formation of gas molecules And a thin film is formed on a workpiece to be heated to a film formation temperature in advance by a vapor phase precursor discharged through the droplet transfer flow path. Through the deposition apparatus, crystalline (eg, polycrystalline) thin films, nanorods, nanowires, or amorphous film growth may be achieved.

The following embodiments are based on the SPD method (or SPD deposition) to economically and easily form a thin film having uniform properties on a workpiece having various areas and shapes, such as a glass window. It may be a precursor supply device, and a thin film forming apparatus using the same.

1A shows a precursor vaporization unit 100 in accordance with an embodiment of the present invention. 1B illustrates a precursor supply apparatus 1000 according to an embodiment of the present invention.

Referring to FIG. 1A, the precursor vaporization unit (or precursor chamber wall 100) includes a chamber wall 120 defining a vaporization space; A droplet inlet (DI) for passing the droplets DR from the droplet supply unit 110 to the vaporization space; A heating unit HP for vaporizing the droplets DR in the vaporization space to form a vapor phase precursor VD; And a carrier gas inlet (GI) for introducing a carrier gas into the vaporization space. And a precursor outlet 400 for outputting the gaseous precursor mixed with the carrier gas to a reaction chamber in which a thin film is formed.

The chamber wall 120 of the vaporization unit 100 has a suitable structure for thermal insulation, sealing, isolation and / or movement of gas to the outside. In other embodiments, chamber wall 120 may be a hood. The hood maintains an atmospheric pressure condition in the vaporization space while preventing heat from leaking from the inside of the vaporization space to the outside during generation of the vapor phase precursor and from leaking and wasting the vapor phase precursor to the outside. The chamber wall 120 may be made of a metallic material made of or coated with a metallic material made of or coated with aluminum, stainless steel, copper, or a refractory metal.

The structure of the chamber wall 120 may have a structure suitable for producing a vapor phase precursor, for example, a circular structure or a square structure, and any other structure. The heating portion HP may be provided with suitable heating means such as an induction heating coil, a resistance wire, or a halogen lamp around the chamber wall 120 for the droplet DR to dry and pyrolyze to form a vapor phase precursor. Can be.

One end of the droplet supply unit 110 is connected to the raw material storage unit (see 200 in FIG. 2), and the other end is connected to the droplet inlet DI of the chamber wall 120 to form droplets DR into the chamber wall 120. ). The generation of the droplets DR uses the surface tension of the liquid raw materials to reduce or interrupt the flow rate of the liquid raw material supplied from the raw material storage unit by the flow rate control means described later, so that the end or the droplets of the tube-shaped droplet supply unit. The end of the inlet may be made in a way to naturally form a liquid raw material in the form of droplets. In another embodiment, the generation of the droplets DR is a liquid raw material in the form of droplets forcibly through the electrode capable of forming an electric field in the droplet supply unit 110 or droplet inlet DI if the piezo element or liquid raw material is ionic. It can be made by a method for discharging the.

The droplets DR in the droplet supply unit 110 may be delivered to the droplet inlet DI under the influence of gravity. To this end, the droplet supply unit 110 may be disposed on the upper side of the droplet inlet DI of the precursor vaporization unit 100 so that the droplets DR may fall vertically into the vaporization space. The droplet supply unit 110 may have a tube shape in order to control the moving speed and the size of the droplet DR, and may include any one or a combination of two or more of a flow control valve, a direction control valve, a piston, and a clamp. Droplet flow control means may be combined. In some embodiments, the droplet supply unit 110 may have a plurality of tubes, and different types of raw materials may be supplied to each droplet supply unit 110 to transfer the plurality of raw materials to the precursor vaporization unit 100.

The outside of the droplet supply unit 110 may include a temperature control means on the wall or inside to heat the inside or maintain a constant temperature to prevent the droplets from condensing to become a contaminant such as particles. The temperature control means may include, for example, an induction heating coil, a resistance wire, or a halogen lamp.

Droplet supply 110 may be formed of a metal conduit or quartz conduit, such as stainless steel, having suitable heat resistance to enable external heating. Alternatively, the droplet supply unit 110 may be formed of a polymer resin material having heat resistance and chemical resistance. In some embodiments, the Teflon material is used to improve chemical resistance and corrosion resistance to the inner surface of the droplet supply unit 110 to secure the mobility in the droplet supply unit 110 and to prevent by-products from being deposited. Coating or water repellent coating for adsorption may be made.

When there are a plurality of droplet supply units 110, there may also be a plurality of droplet inlets DI. The droplet inlet DI may be a hole formed in the first side of the chamber wall 120, for example, the upper side, or the hole. In this case, the droplet supply unit 110 may extend into the vaporization space through the hole to protrude.

In another embodiment, the droplet inlet DI may be in the form of a pipe or nozzle coupled to the chamber wall 120 and projecting into the vaporization space. In this case, the droplet supply unit 110 in the form of a tube may be coupled to the droplet inlet DI to ensure a smooth flow of the droplets or the liquid raw material.

The droplet inlet DI has the same inner diameter size of one end of the droplet supply part 110 side and the opening of the other end of the vaporization space side, or has an inner diameter narrower from the end of the droplet supply part 110 side toward the end of the vaporization space side. Can be lost or large. In one embodiment, by adjusting the size of the inner diameter, it is possible to adjust the size and flow rate of the droplet (DR). For this purpose the inner diameter of the droplet inlet can be in the range of 0.1 mm to 2 cm, for example.

The droplet inlet DI may have suitable sizing means for adjusting the size of the inner diameter of the droplet path to control the size of the droplet DR. For example, the droplet inlet DI may have a bellows structure in which a plurality of partition walls defining the droplet path are positioned to overlap each other and change in size of the inner diameter. Alternatively, when the droplet inlet DI is formed of an elastic polymer resin material, the shape of the inner diameter may be controlled by applying an external force to deform the shape. However, this is merely illustrative and the present invention is not limited thereto. In another embodiment, the droplet inlet DI may have a tube or nozzle shape, in which case a piezo element is coupled to the droplet inlet to adjust the size of the droplets discharged from the droplet inlet by controlling the size of the electrical signal. You can also

In another embodiment, the droplet inlet DI may further include an electrode for applying an electric or magnetic field for controlling the movement of the droplets DR. The electrode may include a coil electrode attached to the droplet inlet DI, a thin film electrode, or a plate electrode spaced apart from the droplet inlet DI, but this is merely an example and the present invention is not limited thereto.

Although the above-described embodiments have described a case in which the droplet inlet DI has a separate configuration from the droplet supply unit 110, the droplet supply unit 110 and the droplet inlet DI may have a single integrated structure. In addition, when the droplet inlet (DI) is a hole formed in one side, for example, the upper side of the chamber wall 120, the tube-shaped droplet supply unit 110 extends through the hole into the interior of the vaporization space In addition, the droplet supply unit 110 may have a droplet shape, in which case a plurality of conduits may be fastened to overlap each other in order to control the characteristics of the droplet inlet DI, for example, the size or flow rate of the droplets. It may comprise a configuration extending in the longitudinal direction and / or an electrode for forming a piezo element or electric field. In addition, the droplet inlet DI and the droplet supply unit 110 may be formed of a metal, quartz, or a polymer resin material having chemical and heat resistance, and these materials are exemplary, but the present invention is not limited thereto.

The heating unit HP may heat the droplets DR discharged from the droplet inlet DI or the droplet supply unit 110 and supplied into the vaporization space to form the vapor phase precursor VD in the vaporization space. The heating unit HP may be any heat energy source capable of vaporizing the droplets DR by heating the inside of the vaporization space through radiation or convection. For example, the heating unit HP may be any one or a combination of two or more of a far infrared heater, an infrared heater, a microwave heater, an induction heater, a dielectric heater, and a resistance heater. The heating unit HP may be coupled to the outside of the chamber wall 120 or may be provided inside the chamber wall 120 to contact the vaporization space.

In addition, the heating unit HP is formed of any one or a combination of a plate form, a container form, a tube form having a through hole through which droplets can pass, a coil form, a rod form, a fullerine and a net form. It can have In one embodiment, when the heating portion HP is in the form of a tube or a fullerene, the droplet DR may be formed into the gaseous precursor VD while passing through the heating portion HP.

The heating unit HP illustrated in FIG. 1A illustrates an induction heating or resistance heating apparatus using a coil in the form of a plate disposed on the bottom of the vaporization space. In this case, heat generated from the heating part HP may be supplied to the droplets DR in a radiation manner, or may be supplied to the droplets DR in a convection manner by a carrier gas in the vaporization space. In this case, the droplets DR may be discharged from the droplet inlet DI or the droplet supply unit 110 or may be vaporized in a non-contact state with the heating unit HP during the drop. In another embodiment, the droplets DR may be dropped and vaporized on the heating portion HP by contacting the heating portion HP, but this is merely illustrative and the present invention is not limited thereto. The heating part HP may be attached on the first surface of the chamber wall 120 or may be mounted outside the chamber wall 120 as shown in FIG. 1B.

The vapor phase precursor VD formed in the vaporization space is mixed with the carrier gas drawn from the carrier gas inlet GI as shown by arrow CG1 and through the precursor outlet 400 in the direction indicated by arrow CG2. It may be delivered to the reaction chamber 500. The carrier gas inlet GI, the droplet inlet DI, the heating unit HP, and the precursor outlet 400 may be disposed to face each other or to overlap at least some of them. Preferably, the gas inlet GI and the precursor outlet 400 may be disposed to face each other, and the droplet inlet DI and the heating part HP may be disposed to face each other.

According to the above-described embodiment, the gaseous precursor is supplied into the vaporization space in the form of droplets DR, not in the form of mist, and by controlling the temperature, the size and / or the moving speed of the droplets DR, in the generation of the gaseous precursor Unnecessary consumption of raw materials can be prevented. In addition, by precisely adjusting the supply rate and the supply amount of the droplets DR according to the deposition rate and the reaction conditions of the deposited thin film, a thin film having uniform characteristics may be provided.

Referring to FIG. 1B, the precursor supply apparatus 1000 may include the precursor vaporization unit 100 described above; A raw material storage unit 200 for storing the liquid raw material in order to supply the liquid raw material to the droplet supply unit 110; A carrier gas storage unit 300 for supplying the carrier gas; A carrier gas supply unit 310 through which the carrier gas passes; And a precursor outlet 400 for delivering the gaseous precursor contained in the carrier gas to the reaction chamber 500. The opening of the precursor outlet 400 may have a shape having a cross section that gradually extends toward the reaction chamber. However, this is exemplary and the present invention is not limited thereto. This will be described in detail with reference to FIGS. 2A to 2B.

The carrier gas reservoir 300 may have a mass flow controller (MFC) and a suitable valve system for controlling the supply flow rate of the carrier gas. The carrier gas supplied from the carrier gas storage part 300 via the carrier gas supply part 310 is mixed with the gaseous precursor in the precursor vaporization part 100 and delivered to the reaction chamber 500. The carrier gas is also heated in the vaporization space, thereby preventing the gaseous precursor VD from being adsorbed to the inner wall of the gaseous precursor VD, for example, the precursor outlet 400, to prevent dust or contamination.

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

2A and 2B are perspective views of precursor outlets 400a and 400b in accordance with various embodiments of the present invention.

Referring to FIG. 2A, in the precursor outlet 400a, an opening area of one end connected to the vaporization space and an opening area of the other end coupled to the reaction chamber may be the same. In another embodiment, referring to FIG. 2B, the precursor outlet 400b may have an array of a plurality of vapor phase precursor flow paths and may be placed in a separate housing for isolation from the outside. In this regard, reference may be made to the applicant's Korean Patent Application No. 10-2014-0056815, the disclosure of which is incorporated herein by reference in its entirety.

The precursor outlets 400, 400a and 400b described above may each be formed of a metal conduit or quartz conduit such as stainless steel having suitable heat resistance to enable external heating. In some embodiments, the inner surface of the precursor outlet may be a coating of Teflon material or a water repellent coating for preventing adsorption to improve chemical resistance and corrosion resistance.

In one embodiment, a heating means may be coupled to the precursor outlet, which may be performed through resistance heating or radiation heating, such as a halogen lamp, which surrounds the resistance wire outside the precursor outlet. As described with reference to FIG. 2B, when the precursor outlet 400b is an array of a plurality of gaseous precursor flow passages, the gaseous precursor flow passages are suitable temperatures for individually controlling the temperature of the droplets therein. Can have a control system. In this case, a resistance heating method may be advantageous in which resistance lines are wrapped around the outside of each of the flow paths and the amount of power supplied may be individually adjusted for each of the flow paths. However, this individual adjustment does not preclude keeping the temperatures of the respective flow paths the same.

3 illustrates a thin film forming apparatus 2000 according to an embodiment of the present invention, and FIGS. 4A and 4B are perspective and side views of the thin film forming apparatus 2000 ′ according to another embodiment of the present invention, respectively. Reference may be made to the foregoing disclosure regarding the constituent members having the same reference numerals as those of FIGS. 1A to 2B among the constituent members of FIGS. 3 to 4B.

Referring to FIG. 3, the thin film forming apparatus 2000 forms a thin film on one surface of the target object SP by the SPD method. The object to be processed SP is a substrate such as glass, ceramic, semiconductor, or metal, which is exemplary and the present invention is not limited thereto. In addition, the surface of the object SP may be smooth or include an uneven pattern such as embossing. For example, the object to be processed SP may be one surface of a low-e glass or a heating glass for forming a planar heating element, and may be a substrate that typically requires a large area thin film.

The thin film forming apparatus 2000 includes a reaction chamber 500 for SPD deposition; A precursor supply device 1000 for generating a vapor phase precursor VD for thin film deposition; And a gas outlet 530. One side of the reaction chamber 500 is combined with the precursor outlet 400 of the precursor supply device 1000 to receive the vapor phase precursor VD. The gaseous precursor VD mixed with the carrier gas may be drawn in the direction of arrow CG2 to form a thin film on the object SP and be discharged in the direction of arrow CG3. The carrier gas outlet 530 may be disposed to face the precursor outlet 400. In one embodiment, the carrier gas discharge unit 530 may be coupled to the collector. The collector suppresses undesired flow, such as vortices and backflow, which are thermal and hydrodynamic non-equilibrium factors in the reaction space within the reaction chamber 500, and thus controls laminar flow, thereby dead spots. ) To achieve a uniform and thin film formation on the large-area workpiece SP without risk of particle formation.

The reaction space of the reaction chamber 500 is defined by the chamber wall, which has a suitable structure for insulation, sealing and / or isolation from the outside. In another embodiment, the chamber wall may be a hood. The hood maintains an atmospheric pressure condition in the reaction space while preventing heat from leaking from the inside of the reaction space to the outside during film formation and preventing the vapor phase precursor from leaking to the outside.

The chamber wall or the hood may be made of aluminum, stainless steel, copper or refractory metal and a material of or coated with a metal material. For example, an anodized or ceramic coated material may be used on the surface of the metal material. As another alternative, the chamber wall or the hood may be fabricated in whole or in part from an electrically insulating material such as quartz, ceramic.

The reaction chamber 500 may be provided with a suitable heater such as an induction heating coil, a resistance wire, or a halogen lamp, to provide a reaction space in which the vapor phase precursor VD is dried and pyrolyzed. In addition, the support chamber PL may be provided in the reaction chamber 500 to mount the object SP, and the support means PL is preferably a resistance heater for temperature control of the object SP. Or heating means by hot fluid and / or cooling means of air cooling, water cooling or semiconductor cooling. For this purpose, the support means PL can be made of aluminum, graphite, alumina or aluminum nitride as a non-limiting example to have a good thermal conductivity and to prevent deformation such as bending of the object SP.

The support means PL may comprise any one or a combination of lift pins, electrostatic chucks and vacuum chucks. In addition, the support means PL may include a device for adjusting the height of the object SP. For example, the height adjustment device may comprise a screw form.

The support means PL may include a rotating body 510 which rotates the object SP for uniform film formation while the thin film forming process for the object SP is performed. The rotating body 510 may be any one or a combination of a non-contact structure capable of rotating by a magnetic field transmitted from an electromagnet or a permanent magnet installed outside the reaction chamber, or a mechanical electric motor using a contact structure. The rotating body 510 may be attached with a separate housing inside or outside the supporting means PL.

The reaction chamber 500 may have a structure suitable for coating the object SP, for example, a circular cylinder structure, a square cylinder structure, and any other structure. The reaction chamber 500 'shown in FIGS. 4A and 4B is a reaction chamber having a hexagonal cylinder structure. In addition, the reaction chamber 500 ′ may include a window 520 for determining a deposition state of an object to be processed.

In an embodiment of the present invention, the FTO transparent conductive film for manufacturing a heat generating window may be formed on the object to be processed using the thin film forming apparatus 2000. By spray pyrolysis, the solution of the FTO precursor is a tin precursor, which is SnCl ₄ 5H ₂ O, (C ₄ H ₉ ) ₂ Sn (CH ₃ COO) ₂ , (CH ₃ ) ₂ SnCl ₂ , or (C ₄ H ₉ ) Compounds such as ₃ SnH may be used and other precursors may be used. As the fluorine precursor, compounds such as NH ₄ F, CF ₃ Br, CF ₂ Cl ₂ , CH ₃ CClF ₂ , CF ₃ COOH, or CH ₃ CHF ₂ can be used. These precursors may be mixed with distilled water or alcohol to have a predetermined weight ratio F / Sn to prepare a mixed solution, and then mounted in the raw material storage unit 200 to generate droplets DR. The FTO thin film may be formed on the glass substrate by spraying the vapor phase precursor through the precursor supply apparatus 1000 after maintaining the temperature of the glass substrate as the object SP.

The present invention described above is not limited to the above-described embodiments and the accompanying drawings, and various substitutions, modifications, and changes are possible within the scope not departing from the technical spirit of the present invention. It will be evident to those who have knowledge of.

According to an embodiment of the present invention, a gaseous precursor supply device capable of easily forming a thin film of uniform characteristics on a workpiece having various areas and shapes while minimizing waste of the liquid raw material for forming a thin film may be provided. have.

In addition, according to an embodiment of the present invention, a thin film forming apparatus capable of easily forming a thin film of uniform characteristics may be provided.

Claims (20)

A precursor supply device coupled to a reaction chamber for forming a thin film on one surface of a workpiece, and supplying a vapor phase precursor for forming the thin film to the reaction chamber, Raw material storage unit for storing the liquid raw material; A droplet supply unit coupled to the raw material storage unit and configured to discharge the liquid raw material in the form of droplets; And A chamber wall defining a vaporization space; A droplet inlet formed on the first side of the chamber wall, through which droplets pass from the droplet supply to the vaporization space; A heating unit coupled to the vaporization space to vaporize the droplets in the vaporization space to form a gaseous precursor in the vaporization space; A carrier gas inlet formed on the second side of the chamber wall for introducing carrier gas into the vaporization space; And a precursor vaporization portion formed on the third side of the chamber wall and including a precursor outlet for outputting the gaseous precursor mixed with the carrier gas to the reaction chamber. The method of claim 1, The droplet supply unit comprises a droplet flow rate control unit for controlling at least one of the moving speed and the size of the droplets. The method of claim 2, And the flow control unit comprises any one or a combination of two or more of a flow control valve, a direction control valve, a piston, and a clamp. The method of claim 1, Precursor supply apparatus is provided with a temperature control means for preventing condensation is generated by the condensation of droplets on the outer wall or inside of the droplet supply. The method of claim 1, And a plurality of droplet supply units, and different types of raw materials are supplied to each droplet supply unit. The method of claim 1, The droplet inlet is a hole, and through the hole the droplet supply unit is extended into the vaporization space protrudes precursor supply apparatus. The method of claim 1, The droplet inlet may be a droplet path or a nozzle coupled to the chamber wall to protrude into the vaporization space, and the droplet supply unit is coupled to the droplet inlet. The method of claim 1, And the first side of the chamber wall to which the droplet supply unit is coupled is an upper side of the chamber wall, and the droplet supply unit extends vertically. The method of claim 1, The droplet supply unit or the droplet inlet has a tube shape, the inner diameter of the precursor supply apparatus is constant, increased or decreased in the extending direction. The method of claim 1, The droplet supply unit or the droplet inlet may reduce or interrupt the flow rate of the liquid raw material supplied from the raw material storage unit by using the surface tension of the liquid raw materials to the end of the droplet supply unit or the droplet inlet. And generating the droplets by a method in which the particles form a droplet. The method of claim 1, The droplet supply part or the droplet inlet is a method of forcibly discharging the liquid raw material in the form of droplets through a piezo element coupled to the droplet supply part or the droplet inlet or an electrode capable of forming an electric field when the liquid raw material is ionic. Precursor supply apparatus for generating droplets. The method of claim 1, The droplet supply unit or the droplet inlet is a precursor supply device for adjusting the size of the droplets by adjusting the size of the inner diameter. The method of claim 1, Wherein the heating unit is a precursor supply device having a form of any one or a combination of plate form, vessel form, tube form having a through hole through which the droplet can pass, coil form, rod form, fullerine and net form. The method of claim 1, And the heating portion is in contact with the vaporization space or coupled to the outside of the chamber wall. The method of claim 1, And the droplet inlet and the heating portion are disposed to face each other. The method of claim 1, And the heating portion comprises any one or a combination of two or more of a far infrared heating device, an infrared heating device, a microwave heating device, an induction heating device, a dielectric heating device, and a resistance heating device. The method of claim 1, The opening of the precursor outlet has a shape having a cross-section gradually extending toward the reaction chamber. A reaction chamber defining a space for forming a thin film on one surface of the workpiece; Support means for placing the object to be processed in the reaction chamber; And A precursor supply device coupled to the reaction chamber for spraying a vapor phase precursor onto one surface of the workpiece, The precursor supply device, Raw material storage unit for storing the liquid raw material; A droplet supply unit coupled to the raw material storage unit and configured to discharge the liquid raw material in the form of droplets; And A chamber wall defining a vaporization space; A droplet inlet formed on the first side of the chamber wall, through which droplets pass from the droplet supply to the vaporization space; A heating unit coupled to the vaporization space to vaporize the droplets in the vaporization space to form a gaseous precursor in the vaporization space; A carrier gas inlet formed on the second side of the chamber wall for introducing carrier gas into the vaporization space; And a precursor supply chamber formed on the third side of the chamber wall and including a precursor outlet for outputting the gaseous precursor mixed with the carrier gas to the reaction chamber. The method of claim 18, And the supporting means includes any one or a combination of a non-contact structure by an electromagnet or a permanent magnet and a mechanical electric motor using a contact structure to rotate the object to be processed. The method of claim 18, And the thin film forming apparatus forms the thin film by spray pyrolysis.

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