KR102233750B1 - Method of forming metal oxide thin film and metal oxide thin film printing apparatus - Google Patents

Abstract

The present invention relates to a method of forming a metal oxide thin film and an apparatus for printing a metal oxide thin film using gas phase jet printing, wherein the method of forming the metal oxide thin film comprises: vaporizing a first metal oxide precursor; Introducing the vaporized first metal oxide precursor into a mixing chamber using a first carrier gas; Spraying the introduced first metal oxide precursor onto a substrate through a micronozzle connected to a lower end of the mixing chamber to form a first metal oxide precursor layer on the substrate; And forming a first metal oxide layer by irradiating an electromagnetic wave to the first metal oxide precursor layer.

Description

TECHNICAL FIELD The method of forming a metal oxide thin film and a metal oxide thin film printing apparatus TECHNICAL FIELD

The present invention relates to a metal oxide thin film forming method and a metal oxide thin film printing apparatus, and more particularly, to a metal oxide thin film forming method and a metal oxide thin film printing apparatus using vapor jet printing.

The metal oxide thin film is widely used as a gate insulating film of a MOSFET as a typical non-conductor, and as a conductor as a transparent electrode for displays and energy devices. Recently, it has been developed a lot as a semiconductor to replace silicon, and is used as a charge transport layer of, for example, a thin film transistor (TFT) for a backplane of an OLED or UD display or a thin film transistor (TFT) of a transparent electronic device. In particular, a zinc oxide (ZnO) thin film among metal oxide materials is a material capable of controlling conductivity and semiconductor properties according to oxygen content or doping material, and thin film transistors using this as a charge transport layer include liquid crystal displays and organic electroluminescent displays. It can be applied to a large area display.

Generally used metal oxide thin films are mainly manufactured by vacuum deposition processes such as sputtering and e-beam. These processes can provide a high-quality oxide film, but since particles having high kinetic energy or high temperature conditions are used, there is a great limitation on a usable lower material or substrate. In addition, there is a problem that an expensive optical etching process is required to form a fine pattern of a metal oxide thin film.

On the other hand, in the case of a CVD process or a PECVD process, it can be performed even in a relatively low vacuum, but a metal oxide thin film is formed by depositing the precursor entirely on the substrate using a shower head. That is, the CVD process or PECVD process also requires a separate patterning process. In addition, since the CVD process or the PECVD process may damage the substrate due to a high energy reaction, it is difficult to apply it to a flexible substrate.

Meanwhile, among printing technologies capable of direct fine patterning, wet-based screen printing, inkjet printing, and offset printing are typically used, and organic materials-based materials are being developed as a process for mass production. In the case of a wet process, the invasion of the substrate by the solvent used is large, and the interference between interlayer materials exists in the laminated structure, so its utilization is limited in a device using a multilayer structure. The organic vapor-jet printing (OVJP) process, which has improved these disadvantages, is a process of heating an organic semiconductor to vaporize it, moving it to a nozzle using an inert carrier gas, and then jetting it. In the case of the gaseous jet method, since a solvent is not used, there are less restrictions on the material and the substrate, and there is no reduction in patterning precision due to the solvent effect generated in the ink jet. However, in the case of metal oxides excluding organic semiconductors, the vaporization temperature of the metal oxides is very high above 1000° C., which can damage the substrate, making it difficult to apply the organic vapor jet printing process to metal oxide thin film formation there is a problem.

The technical problem to be achieved by the present invention is to provide a method of forming a metal oxide thin film that does not require a separate patterning process.

Another technical problem to be achieved by the present invention is to provide a metal oxide thin film printing apparatus for implementing the method of forming the metal oxide thin film.

According to the concept of the present invention, a method of forming a metal oxide thin film includes vaporizing a first metal oxide precursor; Introducing the vaporized first metal oxide precursor into a mixing chamber using a first carrier gas; Spraying the introduced first metal oxide precursor onto a substrate through a micronozzle connected to a lower end of the mixing chamber to form a first metal oxide precursor layer on the substrate; And forming a first metal oxide layer by irradiating an electromagnetic wave to the first metal oxide precursor layer.

The first metal oxide precursor may be an organometallic compound capable of vaporizing at a higher pressure and lower temperature than the first metal oxide including the same metal element as the first metal oxide precursor.

Vaporizing the first metal oxide precursor may include vaporizing the first metal oxide precursor under a condition in which a solvent is not present.

Forming the first metal oxide precursor layer may include spraying the introduced first metal oxide precursor to a first region on the substrate to form the first metal oxide precursor layer on the first region; And spraying the introduced first metal oxide precursor to a second region adjacent to the first region to form a predetermined pattern. In this case, the predetermined pattern may include a first metal oxide precursor layer on the first region and a first metal oxide precursor layer on the second region connected thereto.

The amount of the first metal oxide precursor introduced into the mixing chamber may be adjusted by the flow rate of the first carrier gas.

The electromagnetic wave irradiation may be performed simultaneously with the formation of the first metal oxide precursor layer or after the formation of the first metal oxide precursor layer.

Forming the first metal oxide layer includes irradiating an electromagnetic wave to a predetermined region of the first metal oxide precursor layer to convert a part of the first metal oxide precursor layer into the first metal oxide layer. I can.

The electromagnetic wave may include at least one of ultraviolet rays, infrared rays, visible rays, microwaves, gamma rays, and X rays.

Forming the first metal oxide layer may further include performing post-heat treatment after irradiation with electromagnetic waves.

On the other hand, the method of forming the metal oxide thin film according to the concept of the present invention includes vaporizing a second metal oxide precursor; Introducing the vaporized second metal oxide precursor into a mixing chamber using a second carrier gas; The introduced second metal oxide precursor is sprayed onto the substrate through a micronozzle connected to the lower end of the mixing chamber to form a second metal oxide precursor layer on the first metal oxide precursor layer or the first metal oxide layer. To do; And forming a second metal oxide layer by irradiating an electromagnetic wave to the second metal oxide precursor layer.

Further, the first metal oxide layer formed using the first metal oxide precursor layer and the second metal oxide layer formed using the second metal oxide precursor layer may be sequentially stacked.

According to another concept of the present invention, a method of forming the metal oxide thin film includes vaporizing a first metal oxide precursor and a second metal oxide precursor, respectively; The vaporized first metal oxide precursor and the vaporized second metal oxide precursor are introduced into a mixing chamber using a first carrier gas and a second carrier gas, respectively, so that the first metal oxide precursor and the second metal oxide precursor are Forming a mixture; Spraying the mixture onto a substrate through a micro nozzle connected to a lower end of the mixing chamber to form a composite metal oxide precursor layer on the substrate; And forming a composite metal oxide layer by irradiating an electromagnetic wave to the composite metal oxide precursor layer.

The amount of the first metal oxide precursor and the amount of the second metal oxide precursor introduced into the mixing chamber may be adjusted by a flow rate of the first carrier gas and a flow rate of the second carrier gas, respectively, and the composite metal The composition of the oxide layer may be adjusted by the amount of the first metal oxide precursor and the amount of the second metal oxide precursor introduced into the mixing chamber.

According to the concept of the present invention, a metal oxide thin film printing apparatus includes: a first storage chamber including a first heater for receiving a first metal oxide precursor and vaporizing the first metal oxide precursor; A mixing chamber connected to the first storage chamber, wherein the vaporized first metal oxide precursor is introduced together with a first carrier gas, and the first metal oxide precursor and the first carrier gas move to a micro nozzle connected to the lower end ; A first carrier gas valve controlling an amount of the first metal oxide precursor introduced into the mixing chamber; A micro nozzle spraying the first metal oxide precursor; A first electromagnetic wave irradiator for irradiating an electromagnetic wave for converting the first metal oxide precursor into a first metal oxide; A first stage in which a substrate is loaded and a first metal oxide precursor layer is formed on the substrate; And a second stage in which a first metal oxide layer is formed from the first metal oxide precursor layer by loading the substrate moved from the first stage and irradiating the electromagnetic wave on the substrate.

In this case, the substrate may be a flexible substrate, and the flexible substrate may be moved from the first stage to the second stage by a roll.

Further, a deposition chamber including the first storage chamber, the mixing chamber, the micro nozzle, the first electromagnetic wave irradiator, the first stage and the second stage may be further included therein.

In addition, on the second stage, a second electromagnetic wave irradiator for irradiating electromagnetic waves for selectively heating the first metal oxide precursor layer or the first metal oxide layer may be further included.

The metal oxide thin film printing apparatus according to the concept of the present invention includes: a second storage chamber containing a second metal oxide precursor and having a second heater for vaporizing the second metal oxide precursor; And a second carrier gas valve that adjusts the amount of the second metal oxide precursor introduced into the mixing chamber. In this case, the mixing chamber is connected to the second storage chamber so that the vaporized second metal oxide precursor may be introduced together with a second carrier gas, and the micronozzle is a first metal oxide precursor and a second metal oxide precursor. Alternatively, a mixture of these can be sprayed.

In the mixing chamber, the first metal oxide precursor and the second metal oxide precursor may be mixed, and the micro nozzle may spray a mixture of the first metal oxide precursor and the second metal oxide precursor.

It may further include a controller for individually controlling the first carrier gas valve and the second carrier gas valve.

In the present invention, by performing a vapor phase jet printing process using a metal oxide precursor such as an organometallic compound, a metal oxide thin film can be formed under relatively low deposition conditions compared to the case of using a metal oxide directly. Therefore, substrates or other thin films that are sensitive to process conditions can be used without special restrictions. In addition, according to the present invention, a pattern can be formed immediately by printing a metal oxide thin film without a separate patterning process. Further, it is possible to implement a roll-to-roll process in which a flexible substrate is applied using the low deposition conditions, and increase productivity by performing large-area electromagnetic wave irradiation thereon.

Further, according to the present invention, by using two or more different metal oxide precursors, a metal oxide thin film having a multilayer structure or a composite metal oxide thin film including two or more metal components can be formed in one process. In addition, in the case of the composite metal oxide thin film, its composition can be easily adjusted.

1A is a schematic diagram illustrating an apparatus for printing a metal oxide thin film according to an embodiment of the present invention.
1B is a schematic diagram showing a carrier gas supplier according to an embodiment of the present invention.
1C is a schematic diagram showing an apparatus for printing a metal oxide thin film according to another embodiment of the present invention.
2A is a schematic diagram illustrating an apparatus for printing a metal oxide thin film according to another embodiment of the present invention.
2B is a schematic diagram showing an apparatus for printing a metal oxide thin film according to another embodiment of the present invention.
3 is a flowchart illustrating a method of forming a metal oxide thin film according to an embodiment of the present invention.
4A to 4C are schematic diagrams illustrating a method of forming a patterned metal oxide precursor layer according to an embodiment of the present invention.
5A to 5C are schematic diagrams illustrating a patterning method according to an embodiment of the present invention.
6 is a flowchart illustrating a method of forming a metal oxide thin film according to another embodiment of the present invention.
7A to 7C are cross-sectional views illustrating a method of forming a multilayer structure SS in which a first metal oxide layer and a second metal oxide layer are sequentially stacked according to another embodiment of the present invention.
8 is a flowchart illustrating a method of forming a metal oxide thin film according to another embodiment of the present invention.
9A and 9B are cross-sectional views illustrating a method of forming a composite metal oxide layer according to another embodiment of the present invention.
10A to 10C are cross-sectional views illustrating a method of manufacturing a thin film transistor according to an embodiment of the present invention.
11 is a graph showing the refractive index of each of the thin film of Comparative Example 1 and the thin film of Example 1 according to an experimental example of the present invention.
12 is a graph showing X-ray diffraction analysis results of the thin film of Comparative Example 1 and the thin film of Example 1 according to an experimental example of the present invention.
13 is a graph showing electrical characteristics of the thin film of Example 1 according to an experimental example of the present invention.

The above objects, other objects, features, and advantages of the present invention will be easily understood through the following preferred embodiments related to the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed contents may be thorough and complete, and the spirit of the present invention may be sufficiently conveyed to those skilled in the art.

In this specification, when it is mentioned that a film (or layer) is on another film (or layer) or substrate, it may be formed directly on the other film (or layer) or substrate, or a third film between them (Or a layer) may be interposed. In addition, in the drawings, the size and thickness of components are exaggerated for clarity. In addition, in various embodiments of the present specification, terms such as first, second, and third are used to describe various regions, films (or layers), etc., but these regions and films are limited by these terms. It shouldn't be. These terms are only used to distinguish one region or film (or layer) from another region or film (or layer). Accordingly, the film quality referred to as the first film quality in one embodiment may be referred to as the second film quality in another embodiment. Each embodiment described and illustrated herein also includes its complementary embodiment. In the present specification, the expression'and/or' is used as a meaning including at least one of the elements listed before and after. Parts indicated by the same reference numerals throughout the specification represent the same elements.

Hereinafter, a method of forming a metal oxide thin film, an apparatus for printing a metal oxide thin film, and a method of manufacturing a thin film transistor according to the present invention will be described in detail with reference to the accompanying drawings.

1A is a schematic diagram showing a metal oxide thin film printing apparatus 100 for forming a metal oxide thin film according to an embodiment of the present invention.

Referring to FIG. 1A, the metal oxide thin film printing apparatus 100 includes a first storage chamber 140 accommodating a first metal oxide precursor 2 and a mixing chamber connected to the first storage chamber 140 ( 130), a first carrier gas valve 160 for adjusting the flow rate of the first carrier gas 3, a micro nozzle 120 for injecting the first metal oxide precursor 2, the injected first metal oxide precursor In order to convert (2) into a metal oxide, an electromagnetic wave irradiator 180 for irradiating electromagnetic waves and a stage 110 for loading the substrate 1 may be included. Furthermore, the metal oxide thin film printing apparatus 100 may further include a shell 135 surrounding the first storage chamber 140 and the mixing chamber 130.

The first storage chamber 140 may include a first heater 145 for vaporizing the first metal oxide precursor 2. The first heater 145 may heat the temperature in the first storage chamber 140 to about 500°C. For example, the temperature in the first storage chamber 140 may be reduced to the first metal oxide precursor (2). It can be adjusted to the temperature at which it can be vaporized. Furthermore, the first storage chamber 140 may be formed in plural. Each of the first storage chambers 140 may accommodate the first metal oxide precursor 2 therein.

The vaporized first metal oxide precursor 2 may be introduced into the mixing chamber 130 together with the first carrier gas 3. The first storage chamber 140 and the mixing chamber 130 may be connected to a moving passage 150, and the first metal oxide precursor 2 is transferred to the mixing chamber 130 through the moving passage 150. Can flow into. One axial end (upper end) of the mixing chamber 130 may be connected to a first carrier gas moving passage 155, and the first carrier gas 3 may be transferred to the first carrier gas moving passage 155. It may be introduced into the mixing chamber 130. The first carrier gas valve 160 may be positioned on the first carrier gas movement passage 155, and a first carrier gas introduced into the mixing chamber 130 through the first carrier gas valve 160 (3) The flow rate can be adjusted. Since the amount of the first metal oxide precursor 2 introduced into the mixing chamber 130 can be adjusted by the flow rate of the first carrier gas 3, the first carrier gas valve 160 By using, the amount of the first metal oxide precursor 2 introduced into the mixing chamber 130 may be adjusted.

The other axial end (lower end) of the mixing chamber 130 may be connected to the micro nozzle 120. The first metal oxide precursor 2 moves to the micro-nozzle 120 along the mixing chamber 130 by the first carrier gas 3, and the substrate 1 through the micro-nozzle 120 ) Can be jetted onto. The micro nozzle 120 may include a third heater (not shown). The third heater may heat the temperature in the micro nozzle 120 to a temperature equal to or higher than the temperature in the first storage chamber 140. As a result, the first metal oxide precursor 2 may be cooled while moving the mixing chamber 130 and condensation in the micro nozzle 120 may be prevented. The diameter of the micro nozzle 120 may be changed according to the line width of the first metal oxide precursor layer or the first metal oxide layer 4 to be formed.

The electromagnetic wave irradiator 180 may be located apart from the outer shell 135 and the micro nozzle 120, and irradiates an electromagnetic wave capable of converting the sprayed first metal oxide precursor 2 into a first metal oxide. can do. The electromagnetic wave may include at least one of ultraviolet rays, infrared rays, visible rays, microwaves, gamma rays, and X rays. The electromagnetic wave irradiator 180 may include a large-area light source of a lamp type or a direct light source such as an LED or a laser.

The stage 110 may be located under the micro nozzle 120, and the substrate 1 may be loaded on the top of the stage 110. The substrate 1 may be spaced apart from the micro nozzle 120 by a predetermined distance, and may be positioned between the micro nozzle 120 and the stage 110. On the substrate 1, a first metal oxide precursor layer (not shown) formed from the sprayed first metal oxide precursor 2, or a first metal oxide layer formed from the first metal oxide precursor layer by irradiation with electromagnetic waves ( 4) This can be located.

The stage 110 includes a first direction D1, a second direction D2 crossing the first direction D1, and a first direction D1 and a second direction D2. It can selectively move in three directions (D3). Accordingly, a pattern shape of the first metal oxide layer 4 formed on the substrate 1 may be determined. The formation of a pattern made of the first metal oxide layer 4 will be described later.

The metal oxide thin film printing apparatus 100 may include a carrier gas supplier 170 connected to the first carrier gas movement passage 155. The carrier gas supplier 170 may introduce the first carrier gas 3 into the mixing chamber 130.

1B is a schematic diagram showing the carrier gas supply 170 according to an embodiment of the present invention.

Referring to FIG. 1B, the carrier gas supplier 170 may include a flow meter 171 and a preheater 172. The first carrier gas 3 may pass through the flow meter 171 and the preheater 172 to be introduced into the first carrier gas movement passage 155. The flow meter 171 may monitor the flow rate of the first carrier gas 3, and the preheater 172 may raise the temperature of the first carrier gas 3 to an appropriate temperature.

The metal oxide thin film printing apparatus 100 may include a controller 190 for controlling opening and closing of the first carrier gas valve 160. For example, the controller 190 may control the first carrier gas valve 160 with a digital signal through a pulse generator. Accordingly, the first carrier gas valve 160 may be controlled at high speed.

The controller 190 may control the first heater 145 provided in the first storage chamber 140 and the third heater (not shown) provided in the micro nozzle 120, whereby the The temperature in the first storage chamber 140 and the temperature in the micro nozzle 120 may be controlled. In addition, the first heater 145 and the third heater may be individually controlled so that the temperature in the first storage chamber 140 and the temperature in the micro nozzle 120 may be different from each other.

The controller 190 may control the electromagnetic wave irradiator 180, thereby controlling the frequency, intensity, irradiation time, irradiation area, and the like of the electromagnetic wave emitted from the electromagnetic wave irradiator 180.

The controller 190 may control the stage 110, thereby controlling a moving direction of the stage 110, and the like.

The metal oxide thin film printing apparatus 100 may further include a deposition chamber 300, and the first storage chamber 140, the mixing chamber 130, and the micro nozzle are inside the deposition chamber 300. 120, the electromagnetic wave irradiator 180 and the stage 110 may be located. That is, in the deposition chamber 300, the first metal oxide precursor layer and/or the first metal oxide layer 4 may be formed on the substrate 1. The deposition chamber 300 may provide an environment for forming the first metal oxide precursor layer and/or the first metal oxide precursor layer by separating its inner space from the external environment and disconnecting it from the external environment. Meanwhile, since the first metal oxide precursor 2 is easily vaporizable, the first metal oxide precursor layer and/or the first metal oxide layer 4 may be formed even under relatively low deposition conditions. . The relatively low deposition condition may be a high pressure close to atmospheric pressure and a low temperature of about 200°C or less. There is a problem that the electromagnetic wave irradiator 180 is difficult to be positioned under vacuum or high temperature conditions. Meanwhile, as described above, since the metal oxide thin film printing apparatus 100 according to an embodiment of the present invention can form a thin film under the relatively low deposition condition, the electromagnetic wave irradiator 180 is the deposition chamber 300 ) Can be located inside. Thereby, the electromagnetic wave irradiator 180 interlocks with the micro nozzle 120 to effectively perform the spraying of the first metal oxide precursor 2 and the conversion of the first metal oxide precursor 2 in one device. I can.

The deposition chamber 300 may include a vacuum pump (not shown), and the pressure in the inner space thereof may be adjusted using the vacuum pump. Accordingly, a pressure condition for vaporization and deposition of the first metal oxide precursor 2, for example, a low vacuum condition of 10 mmHg to 760 mmHg can be formed.

1C is a schematic diagram showing a metal oxide thin film printing apparatus 100 ′ for forming a metal oxide thin film according to another embodiment of the present invention. Here, only a configuration different from the metal oxide thin film printing apparatus 100 according to an exemplary embodiment described with reference to FIG. 1A will be described.

Referring to FIG. 1C, an application example of a metal oxide thin film printing apparatus 100' according to an embodiment of the present invention to a roll-to-roll process is shown. Specifically, the metal oxide thin film printing apparatus 100' includes a first stage 110a for loading the substrate 1, a second stage 110b for loading the moved substrate 1, and the second stage ( A first electromagnetic wave irradiator 180a for irradiating electromagnetic waves on the substrate 1 loaded on 110b) may be further included. Further, the substrate 1 may be a flexible substrate. In this case, the metal oxide thin film printing apparatus 100 ′ is a roll for moving the flexible substrate from the first stage 110a to the second stage 110b. It may further include (195). Accordingly, it is possible to implement a roll-to-roll process in which the deposition of the first metal oxide precursor and the conversion of the first metal oxide precursor to the first metal oxide are successively and sequentially performed.

Unlike the metal oxide thin film printing apparatus 100 according to the exemplary embodiment described above, the first stage 110a and the second stage 110b are in the second direction D2 and the third direction D3. You can move selectively. In addition, the first stage 110a and the second stage 110b may be integrated. The substrate 1 may be moved in the first direction D1 by the roll 195. Accordingly, a pattern shape of the first metal oxide layer 4 formed on the substrate 1 may be determined. Alternatively, the micronozzle 120 itself spraying the first metal oxide precursor selectively moves in a first direction D1, a second direction D2, and a third direction D3, while the first metal oxide layer ( The pattern shape of 4) may be determined, and this is not particularly limited.

On the first stage 110a, the first metal oxide precursor may be sprayed onto the loaded substrate 1 to form a first metal oxide precursor layer 4 ′. Thereafter, the substrate 1 on which the first metal oxide precursor layer 4 ′ is formed may be moved onto the second stage 110b.

On the second stage 110b, electromagnetic waves may be irradiated onto the loaded substrate 1 to form a first metal oxide layer 4 from the first metal oxide precursor layer 4 ′. The electromagnetic wave may be irradiated through the first electromagnetic wave irradiator 180a.

The first electromagnetic wave irradiator 180a may include a light source that irradiates electromagnetic waves on the substrate 1 in a large area. In this case, the pattern of the first metal oxide precursor layer 4 ′ formed on the first stage 110a may be collectively converted into a pattern of the first metal oxide layer 4. This can improve the productivity of the process.

The metal oxide thin film printing apparatus 100 ′ generates an electromagnetic wave for selectively heating the first metal oxide precursor layer 4 ′ or the first metal oxide layer 4 on the second stage 110b. It may further include a second electromagnetic wave irradiator (180b) to irradiate. Specifically, the second electromagnetic wave irradiator 180b is disposed in front of the first electromagnetic wave irradiator 180a to selectively heat the first metal oxide precursor layer 4 ′. Alternatively, the second electromagnetic wave irradiator 180b may be disposed at a rear end of the first electromagnetic wave irradiator 180a to selectively heat the first metal oxide layer 4. Accordingly, a conversion rate from the first metal oxide precursor layer 4 ′ to the first metal oxide layer 4 may be further increased. Like the first electromagnetic wave irradiator 180a, the second electromagnetic wave irradiator 180b may irradiate electromagnetic waves on the substrate 1 in a large area. The electromagnetic wave irradiated from the second electromagnetic wave irradiator 180b is visible to selectively increase the temperature of the first metal oxide precursor layer 4 ′ and/or the first metal oxide layer 4 on the substrate 1. It may be a light beam or light in the infrared region. The second electromagnetic wave irradiator 180b may include a flash lamp or a pulse laser.

The metal oxide thin film printing apparatus 100 ′ may further include a deposition chamber 300, and the first storage chamber 140, the mixing chamber 130, and the micro The nozzle 120, the first electromagnetic wave irradiator 180a, the second electromagnetic wave irradiator 180b, the first stage 110a, and the second stage 110b may be positioned. The deposition chamber 300 is the same as the metal oxide thin film printing apparatus 100 according to an embodiment of the present invention described above with reference to FIG. 1A. Since the metal oxide thin film printing apparatus 100 ′ according to an embodiment of the present invention can form a thin film under relatively low deposition conditions, the first electromagnetic wave irradiator 180a and the second electromagnetic wave irradiator 180b are It may be located inside the deposition chamber 300. Accordingly, it is possible to implement a continuous roll-to-roll process in which deposition and conversion of the first metal oxide precursor 2 are performed in one device.

As described above, since the metal oxide thin film printing apparatus 100 ′ according to an embodiment of the present invention can form a thin film under the relatively low deposition condition, the deposition of the first metal oxide precursor and the first metal oxide precursor The conversion to the first metal oxide can be performed in a separate stage. Accordingly, the pattern of the first metal oxide precursor layer 4 ′ may be collectively converted to the pattern of the first metal oxide layer 4 due to the large-area electromagnetic wave irradiation on the second stage 110b.

2A is a schematic diagram showing a metal oxide thin film printing apparatus 200 for forming a metal oxide thin film according to another embodiment of the present invention.

Referring to FIG. 2A, the metal oxide thin film printing apparatus 200 includes a first storage chamber 240a accommodating a first metal oxide precursor 2a and a second storage chamber 2b accommodating a second metal oxide precursor 2b. The chamber 240b, the mixing chamber 230 connected to the first storage chamber 240a and the second storage chamber 240b, and a first carrier gas valve 260a for adjusting the flow rate of the first carrier gas 3a , A second carrier gas valve 260b for controlling the flow rate of the second carrier gas 3b, a micronozzle 220 for injecting metal oxide precursors 2a, 2b, and the injected metal oxide precursors 2a, 2b An electromagnetic wave irradiator 280 for irradiating electromagnetic waves in order to convert to a metal oxide and a stage 210 for loading the substrate 1 may be included. The metal oxide precursors 2a and 2b may include a first metal oxide precursor 2a, a second metal oxide precursor 2b, or a mixture thereof, and the metal oxide includes a first metal oxide precursor 2a. The first metal oxide formed by using, the second metal oxide formed by using the second metal oxide precursor (2b), or a composite formed by using a mixture of the first metal oxide precursor (2a) and the second metal oxide precursor (2b) It may contain a metal oxide.

The first storage chamber 240a may include a first heater 245a for vaporizing the first metal oxide precursor 2a, and the second storage chamber 240b may include the second metal oxide precursor ( It may include a second heater (245b) for vaporizing 2b). The first heater 245a and the second heater 245b may heat the temperature in the first storage chamber 240a and the second storage chamber 240b to about 500°C, respectively. For example, the first heater 245a may adjust the temperature in the first storage chamber 240a to a temperature at which the first metal oxide precursor 2a can vaporize, and the second heater 245b may also 2 The temperature in the storage chamber 240b may be adjusted to a temperature at which the second metal oxide precursor 2b can be vaporized. The first storage chamber 240a may be connected to a first carrier gas movement passage 255a, and the second storage chamber 240b may be connected to a second carrier gas movement passage 255b.

Into the mixing chamber 230, the vaporized first metal oxide precursor 2a may be introduced together with the first carrier gas 3a, and the vaporized second metal oxide precursor 2b is a second carrier gas It can be introduced with (3b). The first storage chamber 240a and the mixing chamber 230 may be connected to a first movement passage 250a, and the second storage chamber 240b and the mixing chamber 230 may be connected to a second movement passage 250b. ) Can be connected. The first carrier gas 3a may be introduced into the first storage chamber 240a through the first carrier gas movement passage 255a, and the introduced first carrier gas 3a is the first storage It may be introduced into the mixing chamber 230 through the first moving passage 250a together with the first metal oxide precursor 2a vaporized in the chamber 240a. The second carrier gas 3b may be introduced into the second storage chamber 240b through the second carrier gas movement passage 255b, and the introduced second carrier gas 3b is the second storage Together with the first metal oxide precursor 2a vaporized in the chamber 240b, it may be introduced into the mixing chamber 230 through the second moving passage 250b.

The first carrier gas valve 260a may be positioned on the first carrier gas moving passage 255a, and the second carrier gas valve 260b may be positioned on the second carrier gas moving passage 255b. have. The flow rate of the first carrier gas 3a introduced into the first storage chamber 240a and the mixing chamber 230 through the first carrier gas valve 260a may be adjusted, and the second carrier gas valve ( Flow rates of the second carrier gas 3b flowing into the second storage chamber 240b and the mixing chamber 230 through 260b may be adjusted. As an example, since the amount of the first metal oxide precursor 2a introduced into the mixing chamber 230 can be adjusted by the flow rate of the first carrier gas 3a, as a result, the first carrier gas valve ( The amount of the first metal oxide precursor 2a flowing into the mixing chamber 230 may be adjusted using 260a). According to the same principle, the amount of the second metal oxide precursor 2b introduced into the mixing chamber 230 may be adjusted using the second carrier gas valve 260b.

One axial end (upper end) of the mixing chamber 230 may be connected to a third carrier gas moving passage 255c, and a third carrier gas 3c is mixed with the third carrier gas moving passage 255c. It may be introduced into the chamber 230. The third carrier gas valve 260c may be positioned on the third carrier gas movement passage 255c, and a third carrier gas introduced into the mixing chamber 230 through the third carrier gas valve 260c The flow rate of (3c) can be adjusted. The third carrier gas 3c may move along the mixing chamber 230 together with the metal oxide precursors 2a and 2b introduced into the mixing chamber 230. For example, by adjusting the flow rate of the third carrier gas 3c, the flow rate of the metal oxide precursors 2a and 2b in the mixing chamber 230 and the injection speed of the micro nozzle 220 are controlled. Can be adjusted.

The other axial end (lower end) of the mixing chamber 230 may be connected to the micro nozzle 220. The metal oxide precursors 2a and 2b move to the micronozzle 220 along the mixing chamber 230 by the third carrier gas 3c, and the substrate 1 through the micronozzle 220 ) Can be jet-injected. More specifically, by the flow rate of the first carrier gas 3a controlled by the first carrier gas valve 260a and the flow rate of the second carrier gas 3b controlled by the second carrier gas valve 260b, the micro The metal oxide precursors 2a and 2b sprayed through the nozzle 220 may be a first metal oxide precursor 2a, a second metal oxide precursor 2b, or a mixture thereof. For example, when the first carrier gas valve 260a is opened and the second carrier gas valve 260b is closed, the first metal oxide precursor 2a may be sprayed through the micro nozzle 220. . When the first carrier gas valve 260a is opened and the second carrier gas valve 260b is opened, the first metal oxide precursor 2a and the second metal oxide precursor 2b through the micro nozzle 220 A mixture of can be sprayed.

The micro nozzle 220 may include a third heater (not shown). The third heater may heat the temperature in the micro nozzle 220 to a temperature equal to or higher than the temperature in the first storage chamber 240a or the temperature in the second storage chamber 240b. As a result, the metal oxide precursors 2a and 2b are cooled through the mixing chamber 230 and condensation in the micro nozzle 220 may be prevented. The diameter of the micro nozzle 220 may be changed according to the line width of the metal oxide precursor layer or the metal oxide layers 4a and 4b to be formed.

The electromagnetic wave irradiator 280 may be located spaced apart from the mixing chamber 230 and the micro nozzle 220, and irradiates an electromagnetic wave capable of converting the sprayed metal oxide precursors 2a and 2b into metal oxide. I can. This is as described above with reference to FIG. 1A.

The stage 210 may be located under the micro nozzle 220, and the substrate 1 may be loaded on the stage 210. The substrate 1 may be spaced apart from the micro nozzle 220 by a predetermined distance, and may be positioned between the micro nozzle 220 and the stage 210. A metal oxide precursor layer formed from the sprayed metal oxide precursors 2a and 2b, or a metal oxide layer 4a and 4b formed from the metal oxide precursor layer by irradiation with electromagnetic waves may be positioned on the substrate 1. The metal oxide precursor layer includes a first metal oxide precursor layer formed from a first metal oxide precursor 2a, a second metal oxide precursor layer formed from a second metal oxide precursor 2b, a first metal oxide precursor 2a, and a second metal oxide precursor layer. It may include a composite metal oxide precursor layer formed from a mixture of 2 metal oxide precursors (2b). The metal oxide layers 4a and 4b include a first metal oxide layer 4a formed from the first metal oxide precursor layer, a second metal oxide layer 4b formed from the second metal oxide precursor layer, and the composite metal oxide. It may include a composite metal oxide layer formed from the precursor layer.

The stage 210 may selectively move in a first direction D1, a second direction D2, and a third direction D3. Accordingly, a pattern shape of the metal oxide layers 4a and 4b formed on the substrate 1 may be determined.

The metal oxide thin film printing apparatus 200 includes a first carrier gas supply unit 270a connected to the first carrier gas movement passage 255a, and a second carrier gas supply unit connected to the second carrier gas movement passage 255b. (270b), it may include a third carrier gas supply (270c) connected to the third carrier gas movement passage (255c). Each of the first carrier gas supplier 270a, the second carrier gas supplier 270b, and the third carrier gas supplier 270c is the same as the carrier gas supplier 170 described above with reference to FIGS. 1A and 1B.

The metal oxide thin film printing apparatus 200 includes a controller 290 for controlling the opening and closing of each of the first carrier gas valve 260a, the second carrier gas valve 260b, and the third carrier gas valve 260c. Can include. The controller 290 may individually control the first carrier gas valve 260a, the second carrier gas valve 260b, and the third carrier gas valve 260c, and thus, through the micronozzle 220 The composition of the sprayed metal oxide precursors 2a and 2b may be controlled. As described above, the controller 290 may open the first carrier gas valve 260a to allow the first metal oxide precursor 2a to be injected, or the first carrier gas valve 260a and the All of the second carrier gas valves 260b may be opened to allow a mixture of the first metal oxide precursor 2a and the second metal oxide precursor 2b to be injected. Further, by controlling the first carrier gas valve (260a) and the second carrier gas valve (260b) to control the flow rate of the first carrier gas (3a) and the second carrier gas (3b), and consequently the The composition of the mixture of the first metal oxide precursor 2a and the second metal oxide precursor 2b may be controlled. For example, the controller 290 may control the first carrier gas valve 260a, the second carrier gas valve 260b, and the third carrier gas valve 260c at high speed through a digital signal through a pulse generator. have.

The controller 290 includes the first heater 245a provided in the first storage chamber 240a, the second heater 245b provided in the second storage chamber 240b, and the micro nozzle 220. Each of the provided third heaters (not shown) may be controlled. This is as described above with reference to FIG. 1A.

The controller 290 may control the electromagnetic wave irradiator 280, as described above with reference to FIG. 1A.

The controller 290 may control the stage 210, as described above with reference to FIG. 1A.

The metal oxide thin film printing apparatus 200 may further include a deposition chamber 400, as described above with reference to FIG. 1A. The first storage chamber 240a, the second storage chamber 240b, the mixing chamber 230, the micro nozzle 220, the electromagnetic wave irradiator 280, and the stage 210 are located inside the deposition chamber 400 can do. Furthermore, the deposition chamber 400 may include a vacuum pump (not shown) for adjusting the pressure in the inner space thereof.

2B is a schematic diagram showing a metal oxide thin film printing apparatus 200 ′ for forming a metal oxide thin film according to another embodiment of the present invention. Here, only a configuration different from the metal oxide thin film printing apparatus 200 according to an exemplary embodiment described with reference to FIG. 2A will be described.

Referring to FIG. 2B, an application example of a metal oxide thin film printing apparatus 200' according to an embodiment of the present invention to a roll-to-roll process is shown. Specifically, the metal oxide thin film printing apparatus 200 ′ includes a first stage 210a for loading the substrate 1, a second stage 210b for loading the moved substrate 1, and the second stage ( A first electromagnetic wave irradiator 280a for irradiating electromagnetic waves on the substrate 1 loaded on 210b) may be further included. Further, the substrate 1 may be a flexible substrate. In this case, the metal oxide thin film printing apparatus 200 ′ is a roll for moving the flexible substrate from the first stage 210a to the second stage 210b. It may further include (295). Accordingly, it is possible to implement a roll-to-roll process in which the deposition of the metal oxide precursor and the conversion of the metal oxide precursor to the metal oxide are successively and sequentially performed. The first stage 210a, the second stage 210b, the first electromagnetic wave irradiator 280a, and the roll 295 are similar to the case of the metal oxide thin film printing apparatus 100' previously described with reference to FIG. 1C. same.

On the first stage 210a, the metal oxide precursor is sprayed onto the loaded substrate 1 to form metal oxide precursor layers 4a' and 4b'. Thereafter, the substrate 1 on which the metal oxide precursor layers 4a' and 4b' are formed may be moved onto the second stage 110b. The metal oxide precursor layers 4a' and 4b' are a first metal oxide precursor layer 4a' formed from a first metal oxide precursor 2a, a second metal oxide precursor layer formed from a second metal oxide precursor 2b (4b'), a composite metal oxide precursor layer formed from a mixture of the first metal oxide precursor 2a and the second metal oxide precursor 2b may be included.

On the second stage 210b, an electromagnetic wave is irradiated onto the loaded substrate 1 to form metal oxide layers 4a and 4b from the metal oxide precursor layers 4a' and 4b'. The electromagnetic wave may be irradiated through the first electromagnetic wave irradiator 280a. The metal oxide layers 4a and 4b are a first metal oxide layer 4a formed from the first metal oxide precursor layer 4a', and a second metal oxide layer formed from the second metal oxide precursor layer 4b' (4b) and a composite metal oxide layer formed from the composite metal oxide precursor layer.

The metal oxide thin film printing apparatus 200 ′ is an electromagnetic wave for selectively heating the metal oxide precursor layers 4a ′ and 4b ′ or the metal oxide layers 4a and 4b on the second stage 210b. It may further include a second electromagnetic wave irradiator (280b) to irradiate. The second electromagnetic wave irradiator 280b is the same as the case of the metal oxide thin film printing apparatus 100 ′ described above with reference to FIG. 1C.

The metal oxide thin film printing apparatus 200 ′ may further include a deposition chamber 400, and the first storage chamber 240a, the second storage chamber 240b, and the inside of the deposition chamber 400 Where the mixing chamber 230, the micro nozzle 220, the first electromagnetic wave irradiator 280a, the second electromagnetic wave irradiator 280b, the first stage 210a, and the second stage 210b are located. I can. The deposition chamber 400 is the same as the metal oxide thin film printing apparatus 200 according to an embodiment of the present invention described above with reference to FIG. 2A. Since the metal oxide thin film printing apparatus 400 ′ according to an embodiment of the present invention can form a thin film under relatively low deposition conditions, the first electromagnetic wave irradiator 280a and the second electromagnetic wave irradiator 280b are It may be located inside the deposition chamber 400. Accordingly, it is possible to implement a continuous roll-to-roll process in which deposition and conversion of the metal oxide precursors 2a and 2b are performed in one device.

3 is a flowchart illustrating a method of forming a metal oxide thin film according to an embodiment of the present invention.

1A and 3, the first metal oxide precursor 2 may be vaporized (S100 ). The first metal oxide precursor 2 is a material that can be converted to a first metal oxide when an electromagnetic wave such as ultraviolet rays is applied, and specifically, an organic metal capable of vaporizing at a higher pressure and lower temperature than the first metal oxide. It can be a compound. Here, the first metal oxide may be a metal oxide including the same metal element as the first metal oxide precursor 2. In general, in order to vaporize a metal oxide, a high vacuum condition of 10 mmHg or less and a high temperature condition of 1000°C or more are required. Therefore, when gas phase jet printing is performed using the metal oxide directly, there is a problem that the substrate or the thin film may be damaged due to the high temperature of the sprayed metal oxide. However, in order to vaporize the organometallic compound including C, H, O, etc. in the molecule, it is possible not only under a high vacuum condition of 10 mmHg or less, but also under a low vacuum condition of 10 mmHg to 760 mmHg and a low temperature condition of 400° C. or less. Accordingly, the first metal oxide precursor 2 may be vaporizable at a higher pressure and a lower temperature as compared to a case where the first metal oxide is directly vaporized. In addition, in gas phase jet printing, since the temperature of the sprayed first metal oxide precursor 2 is relatively low, it may not damage the substrate or the thin film.

For example, the first metal oxide precursor 2 may be zinc acetylacetonate, and when the zinc acetylacetonate is irradiated with ultraviolet rays, it may be converted to zinc oxide (ZnO).

The first metal oxide precursor 2 may be accommodated in the first storage chamber 140 and heated by a first heater 145 provided in the first storage chamber 140. When the first metal oxide precursor 2 is heated above its vaporization temperature, the first metal oxide precursor 2 may be vaporized in the first storage chamber 140.

Vaporizing the first metal oxide precursor 2 may include vaporizing the first metal oxide precursor 2 in the absence of a solvent. That is, the first metal oxide precursor 2 is not accommodated in the first storage chamber 140 in the state of a solution to which a solvent is added, but only the first metal oxide precursor 2 is the first storage chamber without a solvent. It can be accommodated within 140. When the first metal oxide precursor 2 is vaporized without an additional solvent, impurities may not be additionally included in the formation of the first metal oxide layer 4 to be described later. In addition, in the gas phase jet printing process, as the sprayed droplets are dried, a coffee stain effect may occur in which a pattern having a peripheral edge thicker than that of the center portion is formed. Since there is no additional solvent, the coffee stain effect can be prevented.

1A and 3, the vaporized first metal oxide precursor 2 may be introduced into the mixing chamber 130 using a first carrier gas 3 (S110). The vaporized first metal oxide precursor 2 may move to the mixing chamber 130 through a moving passage 150 located between the first storage chamber 140 and the mixing chamber 130. In this case, the first carrier gas 3 may flow into the mixing chamber 130 to move the first metal oxide precursor 2. With this principle, the amount of the first metal oxide precursor 2 introduced into the mixing chamber 130 may be adjusted by the flow rate of the first carrier gas 3. The amount of the first metal oxide precursor 2 introduced into the mixing chamber 130 is the injection amount of the first metal oxide precursor 2 to be described later and the deposition amount of the first metal oxide precursor 2 on the substrate 1 Correspondingly, the injection amount and the deposition amount can be adjusted by the flow rate of the first carrier gas 3. Additionally, by increasing the temperature in the first storage chamber 140 or lowering the process pressure to increase the amount of vaporization of the first metal oxide precursor 2, the amount of the introduced first metal oxide precursor 2 may be increased. have.

The first carrier gas 3 may be an inert gas, and may include, for example, at least one of helium, nitrogen, and argon.

1A and 3, the introduced first metal oxide precursor 2 may be sprayed onto the substrate 1 through the micro nozzle 120 connected to the lower end of the mixing chamber 130 (S120). ). Subsequently, a first metal oxide precursor layer may be formed from the first metal oxide precursor 2 sprayed on the substrate 1 (S130).

The first metal oxide precursor 2 may move to the micro nozzle 120 along the mixing chamber 130 by the first carrier gas 3. Subsequently, the first metal oxide precursor 2 may be jet-injected onto the substrate 1 through the micro nozzle 120 by the first carrier gas 3. The micro nozzle 120 may include a third heater (not shown), and condensation of the first metal oxide precursor 2 may be prevented by using the third heater.

The first metal oxide precursor 2 sprayed from the micro nozzle 120 is cooled and condensed to form the first metal oxide precursor layer on the substrate 1. The first metal oxide precursor layer may be a zinc acetylacetonate layer. The first metal oxide precursor layer may be formed by cooling the sprayed first metal oxide precursor 2 by itself without additional heat treatment on the substrate 1. As described above, since the sublimation temperature of the first metal oxide precursor 2 is considerably lower than the sublimation temperature of the first metal oxide, the first metal oxide precursor layer does not cause thermal damage on the substrate 1. Can be formed.

4A to 4C are schematic diagrams illustrating a method of forming a patterned first metal oxide precursor layer.

Referring to FIG. 4A, a pattern region P of a first metal oxide precursor layer to be formed may be defined. The pattern area P may include the first area A1 and the second area A2. As an example, the pattern region P may be defined in an L shape on the substrate 1, and the pattern region P is the first region A1 and the first region extending in a first direction D1. And the second area A2 extending in the second direction D2 while being in contact with the first area A1.

Referring to FIG. 4B, a first metal oxide precursor layer 4 ′ may be sequentially formed on each of the first region A1 and the second region A2. The first metal oxide precursor layer 4 ′ may be formed by depositing the first metal oxide precursor 2 sprayed from the micro nozzle 120 on the surface of the substrate 1. For example, when the first metal oxide precursor layer 4 ′ is formed on the first region A1 in the first direction D1, the substrate 1 is formed in a direction opposite to the first direction D1. Can be formed while moving to. Subsequently, when the first metal oxide precursor layer 4 ′ is formed in the second direction D2 on the second region A2, the substrate 1 is moved in a direction opposite to the second direction D2. It can be formed while making.

Referring to FIG. 4C, the predetermined pattern 4'P may be formed on the pattern area P. For example, referring again to FIG. 4B, the predetermined pattern 4'P is formed on the first metal oxide precursor layer 4'and the second area A2. The first metal oxide precursor layer 4 ′ may be connected.

In the method of forming a metal oxide thin film according to the present invention, since the first metal oxide precursor 2 is sprayed from the micro nozzle 120 as described above, the first metal oxide precursor layer is locally applied on the substrate 1. It can be formed by Accordingly, a patterned first metal oxide precursor layer may be formed without a separate patterning process, and a patterned first metal oxide layer may be formed therefrom.

1A and 3, the first metal oxide layer 4 may be formed by irradiating an electromagnetic wave to the first metal oxide precursor layer (S140 ). When electromagnetic waves are irradiated to the first metal oxide precursor layer, the first metal oxide layer 4 may be formed while C and H inside the first metal oxide precursor layer are separated. For example, when the first metal oxide precursor layer is a zinc acetylacetonate layer, a zinc oxide layer may be formed by irradiating ultraviolet rays on the zinc acetylacetonate layer, as shown in Scheme 1 below.

[Scheme 1]

Zn(C ₅ H ₇ O ₂ ) ₂ (S) H ₂ O → ZnO(S)+2C ₅ H ₈ O ₂ (g)

The electromagnetic wave may include at least one of ultraviolet rays, infrared rays, visible rays, microwaves, gamma rays, and X rays, and may be appropriately selected and used by a person skilled in the art according to the type of the first metal oxide precursor 2.

The electromagnetic wave may be irradiated simultaneously with the formation of the first metal oxide precursor layer or after the formation of the first metal oxide precursor layer. For example, when the electromagnetic wave is irradiated with the formation of the first metal oxide precursor layer, the first metal oxide precursor layer may be deposited and simultaneously converted to the first metal oxide layer 4. As another example, when the electromagnetic wave is irradiated after the formation of the first metal oxide precursor layer, the electromagnetic wave may be irradiated as a post-process after the first metal oxide precursor layer is formed in a desired region. In this case, only one of the metal oxide precursor layers of the multilayer structure stacked on the substrate 1 may be selectively converted into the metal oxide layer. Alternatively, from a plan view, only a partial region of the formed metal oxide precursor layer may be converted into the metal oxide layer. The latter case will be described in more detail as follows.

5A to 5C are schematic diagrams illustrating a patterning method in which only a partial region of the formed metal oxide precursor layer is converted into a first metal oxide layer.

Referring to FIG. 5A, a first metal oxide precursor layer 4 ′ may be formed on the substrate 1. The first metal oxide precursor layer 4 ′ may be formed by depositing the first metal oxide precursor 2 sprayed from the micro nozzle 120 on the surface of the substrate 1.

Referring to FIG. 5B, after the first metal oxide precursor layer 4 ′ is formed, an electromagnetic wave may be irradiated to a predetermined region A3 of the first metal oxide precursor layer 4 ′. The predetermined region A3 may be defined according to a desired pattern shape of the first metal oxide layer 4. The electromagnetic wave may be irradiated through the electromagnetic wave irradiator 180. For example, when the electromagnetic wave is irradiated to the predetermined region A3 extending in the first direction D1, the substrate 1 may be irradiated while moving in a direction opposite to the first direction D1.

Referring to FIG. 5C, a pattern P3 corresponding to the predetermined area A3 may be formed. The pattern P3 is irradiated with an electromagnetic wave on the predetermined area A3, so that the first metal oxide precursor layer 4 ′ on the predetermined area A3 is converted to the first metal oxide layer 4. Can be. Since the first metal oxide precursor layer 4 ′ on the region to which the electromagnetic wave is not irradiated is maintained as it is, a region other than the predetermined region A3 may be an unconverted first metal oxide precursor layer 4 ′. .

In the method of forming a metal oxide thin film according to the present invention, a desired metal oxide pattern can be formed only by post-treating the electromagnetic wave as described above. Therefore, it is possible to effectively form a complex pattern without additionally undergoing an etching process such as a photolithography process using a mask.

Forming the first metal oxide layer 4 may further include performing post-heat treatment after irradiation with electromagnetic waves. Through the post-heat treatment, a conversion rate from the first metal oxide precursor layer to the first metal oxide layer 4 may be further increased.

Further, referring to FIGS. 1C and 3, the substrate 1 may be a flexible substrate. When the substrate 1 is a flexible substrate, the method of forming a metal oxide thin film according to the present invention may be applied to a roll-to-roll process. The method of forming a metal oxide thin film according to the present invention can be applied to a flexible substrate because the thin film is formed under relatively low deposition conditions, and further, since it is possible to form a patterned metal oxide thin film in one process, the roll-to- -May be suitable for roll process. First, the introduced first metal oxide precursor 2 may be sprayed onto the substrate 1 of the first stage 110a through the micro nozzle 120 (S120). Subsequently, a first metal oxide precursor layer 4 ′ may be formed from the first metal oxide precursor 2 sprayed on the substrate 1 (S130 ).

The substrate 1 on which the first metal oxide precursor layer 4 ′ is formed may move in a direction opposite to the first direction D1 by rotation of the roll 195. The moved substrate 1 may be loaded on the second stage 110b. Subsequently, the first metal oxide layer 4 may be formed by irradiating an electromagnetic wave to the first metal oxide precursor layer (S140). That is, the electromagnetic wave may be irradiated after the first metal oxide precursor layer 4 ′ is formed. In addition, the electromagnetic wave may be irradiated in a large area on the entire surface of the substrate 1. As a result, the first metal oxide precursor layer 4 ′ on the substrate 1 may be converted into the first metal oxide layer 4 at a time. The electromagnetic wave may be irradiated by the first electromagnetic wave irradiator 180a.

Further, by using another electromagnetic wave, the first metal oxide precursor layer 4 ′ or the first metal oxide layer 4 may be selectively heated on the second stage 110b. Accordingly, a conversion rate from the first metal oxide precursor layer 4 ′ to the first metal oxide layer 4 may be further increased. The other electromagnetic wave may be irradiated through the second electromagnetic wave irradiator 180b, and may be irradiated on the substrate 1 in a large area. Unlike the first electromagnetic wave, the electromagnetic wave irradiated from the second electromagnetic wave irradiator 180b increases the temperature of the first metal oxide precursor layer 4 ′ and/or the first metal oxide layer 4 on the substrate 1. It may be light in the visible or infrared region that can be selectively raised. In particular, the second electromagnetic wave irradiator 180b may include a flash lamp or a pulse laser, and in this case, the first metal oxide precursor layer 4 ′ and/or the first metal By efficiently and instantaneously controlling the temperature of the oxide layer 4, a thermal effect applied to the entire substrate 1 can be minimized. In addition, since the method of forming a metal oxide thin film according to an embodiment of the present invention is an atmospheric pressure process, unlike the area on the first stage 110a where the micro nozzle 120 is located, the electromagnetic wave irradiators 180a and 180b In the area on the second stage 110b where) is located, the meteorological atmosphere can be adjusted step by step. Accordingly, it is possible to more effectively induce chemical conversion of the deposited first metal oxide precursor layer 4 ′ into the first metal oxide layer 4. For example, when an oxidizing gas such as oxygen, nitrogen dioxide, or ozone that can promote oxidation is passed through the region on the second stage 110b, efficient conversion to metal oxide in a lower temperature atmosphere may be possible.

6 is a flowchart illustrating a method of forming a metal oxide thin film according to another embodiment of the present invention.

2A and 6, the first metal oxide precursor 2a may be vaporized (S200 ). The vaporized first metal oxide precursor 2a may be introduced into the mixing chamber 230 using a first carrier gas 3a (S210). The introduced first metal oxide precursor 2a may be sprayed onto the substrate 1 through the micro nozzle 220 connected to the lower end of the mixing chamber 230 (S220). Subsequently, a first metal oxide precursor layer may be formed from the first metal oxide precursor 2a sprayed on the substrate 1 (S230). The first metal oxide layer 4a may be formed by irradiating an electromagnetic wave to the first metal oxide precursor layer (S240). S200 to S240 are the same as the method of forming a metal oxide thin film according to an embodiment of the present invention described above with reference to FIGS. 1A and 3.

The second metal oxide precursor layer may be vaporized (S250). The vaporized second metal oxide precursor 2b may be introduced into the mixing chamber 230 using a second carrier gas 3b (S260). The introduced second metal oxide precursor 2b may be sprayed onto the first metal oxide layer 4a through the micro nozzle 220 connected to the lower end of the mixing chamber 230 (S270). A first metal oxide precursor layer may be formed on the first metal oxide layer 4a from the sprayed second metal oxide precursor 2b (S280). The second metal oxide layer 4b may be formed by irradiating an electromagnetic wave to the second metal oxide precursor layer (S290). S250 to S290 are the same as the method of forming a metal oxide thin film according to an embodiment of the present invention described above with reference to FIGS. 1A and 3.

The second metal oxide precursor 2b is the same as the first metal oxide precursor 2a described in the exemplary embodiment of the present invention. However, the second metal oxide precursor 2b may be a material different from the first metal oxide precursor 2a. For example, the first metal oxide precursor 2a may be zinc acetylacetonate, and the The second metal oxide precursor 2b may be indium acetylacetonate. When the indium acetylacetonate is irradiated with ultraviolet rays, it may be converted to _{indium oxide (In 2} O _{3 ).}

Through the S200 to S240, the first metal oxide layer 4a is first formed on the substrate 1, and then the second metal oxide layer on the first metal oxide layer 4a through the S250 to S290. (4b) can be formed. That is, the first metal oxide layer 4a formed using the first metal oxide precursor layer and the second metal oxide layer 4b formed using the second metal oxide precursor layer are sequentially stacked multilayer structures Can be formed. This will be described in more detail as follows.

7A to 7C are cross-sectional views illustrating a method of forming a multilayer structure SS in which a first metal oxide layer 4a and a second metal oxide layer 4b are sequentially stacked.

2A and 7A, a first metal oxide layer 4a may be formed on the substrate 1. Forming the first metal oxide layer 4a may include performing the S200 to S240. When the first metal oxide layer 4a is formed, only the first metal oxide precursor 2a may be sprayed from the micro nozzle 220. Specifically, by closing the second carrier gas valve 260b to block the second metal oxide precursor 2b from flowing into the mixing chamber 230, only the first metal oxide precursor 2a is the micronozzle ( 220). As another example, although not shown, the first metal oxide precursor layer may be formed by not performing a separate electromagnetic wave treatment after spraying the first metal oxide precursor 2a onto the substrate 1. Thereafter, a second metal oxide layer 4b may be formed on the first metal oxide precursor layer.

2A and 7B, a second metal oxide layer 4b may be formed on the first metal oxide layer 4a. Forming the second metal oxide layer 4b may include performing S250 to S290. When the second metal oxide layer 4b is formed, only the second metal oxide precursor 2b may be sprayed from the micro nozzle 220. Specifically, by closing the first carrier gas valve 260a to block the first metal oxide precursor 2a from flowing into the mixing chamber 230, only the second metal oxide precursor 2b is the micronozzle ( 220).

2A and 7C, a multilayer structure SS in which the first metal oxide layer 4a and the second metal oxide layer 4b are sequentially stacked may be formed. As another example, although not shown, other layers may be interposed between the first metal oxide layer 4a and the second metal oxide layer 4b. In this case, after the first metal oxide layer 4a is formed and the other layers are formed, the second metal oxide layer 4b may be formed by being spaced apart from the first metal oxide layer 4a. .

Further, referring to FIGS. 2B and 6, the substrate 1 may be a flexible substrate. When the substrate 1 is a flexible substrate, the method of forming a metal oxide thin film according to the present invention may be applied to a roll-to-roll process. This is the same as the method of forming a metal oxide thin film according to an embodiment of the present invention described above with reference to FIGS. 1C and 3.

8 is a flowchart illustrating a method of forming a metal oxide thin film according to another embodiment of the present invention.

9A and 9B are cross-sectional views illustrating a method of forming the composite metal oxide layer 14 on the substrate 1.

Referring to FIGS. 2A and 8, each of the first metal oxide precursor 2a and the second metal oxide precursor 2b may be vaporized (S300 ). The first metal oxide precursor 2a and the second metal oxide precursor 2b are the same as described in another embodiment of the present invention. For example, the first metal oxide precursor 2a may be zinc acetylacetonate, and the second metal oxide precursor 2b may be indium acetylacetonate.

The first metal oxide precursor 2a and the second metal oxide precursor 2b may be accommodated in the first storage chamber 240a and the second storage chamber 240b, respectively. The first metal oxide precursor 2a may be heated by a first heater 245a provided in the first storage chamber 240a, and the second metal oxide precursor 2b is the second storage chamber ( It may be heated through the second heater 245b provided in 240b).

Vaporizing the first metal oxide precursor (2a) and the second metal oxide precursor (2b) is, respectively, the first metal oxide precursor (2a) and the second metal oxide precursor (2b) in the absence of a solvent. It may include vaporizing.

2A and 8, the vaporized first metal oxide precursor (2a) and the vaporized second metal oxide precursor (2b) are respectively used as a first carrier gas (3a) and a second carrier gas (3b). It can be introduced into the mixing chamber 230 by using (S310). The vaporized first metal oxide precursor 2a may move to the mixing chamber 230 through a first moving passage 250a located between the first storage chamber 240a and the mixing chamber 230, The vaporized second metal oxide precursor 2b may move to the mixing chamber 230 through a second movement passage 250b positioned between the second storage chamber 240b and the mixing chamber 230. At this time, the first carrier gas 3a may move the first metal oxide precursor 2a while sequentially flowing through the first storage chamber 240a and the mixing chamber 230, and the second carrier The gas 3b may move the second metal oxide precursor 2b while sequentially flowing through the second storage chamber 240b and the mixing chamber 230.

The amount of the first metal oxide precursor 2a flowing into the mixing chamber 230 and the amount of the second metal oxide precursor 2b flowing into the mixing chamber 230 may be adjusted in the following manner. .

For example, the first carrier gas valve 260a and the second carrier gas valve 260b control the opening/closing cycle per unit time, the number of opening/closing cycles, or the opening/closing time ratio, (3b) Each flow rate and movement can be controlled. Accordingly, the amount of the first metal oxide precursor 2a and the amount of the second metal oxide precursor 2b flowing into the mixing chamber 230 may be selectively adjusted. The first carrier gas valve 260a and the second carrier gas valve 260b may be individually controlled using the controller 290.

As another example, by adjusting the flow rates of each of the first carrier gas 3a flowing into the first storage chamber 240a and the second carrier gas 3b flowing into the second storage chamber 240b, the mixing chamber The amount of the first metal oxide precursor 2a and the amount of the second metal oxide precursor 2b flowing into the 230 may be selectively adjusted. The flow rates of the first carrier gas 3a and the second carrier gas 3b may be adjusted using the first carrier gas supplier 270a and the second carrier gas supplier 270b. Alternatively, it may be adjusted by controlling the first carrier gas valve 260a and the second carrier gas valve 260b.

As another example, by controlling the internal temperature of each of the first storage chamber 240a and the second storage chamber 240b, the amount of the sublimated first metal oxide precursor 2a and the sublimated second metal oxide precursor 2b You can adjust the amount of) respectively. Alternatively, the amount of the first metal oxide precursor 2a sublimated and the amount of the second metal oxide precursor 2b sublimated by adjusting the pressure of each of the first storage chamber 240a and the second storage chamber 240b Each can be adjusted. For example, the first storage chamber 240a may include a first heater 245a, and the second storage chamber 240b may include a second heater 245b. Each of the first heater 245a and the second heater 245b may be individually controlled by the controller 290, thereby controlling the amount of the sublimated first and second metal oxide precursors 2b. As the amount of the sublimated first and second metal oxide precursors 2b increases, the amount of the first and second metal oxide precursors 2b flowing into the mixing chamber 230 may increase.

Through the above-described methods, the ratio of the first metal oxide precursor 2a and the second metal oxide precursor 2b introduced into the mixing chamber 230 may be adjusted.

The first metal oxide precursor 2a and the second metal oxide precursor 2b introduced into the mixing chamber 230 may be uniformly mixed with each other while moving in the mixing chamber 230. As a result, a mixture of the first metal oxide precursor 2a and the second metal oxide precursor 2b may be formed in the mixing chamber 230. The composition of the mixture may be determined according to the ratio of the introduced first metal oxide precursor 2a and the second metal oxide precursor 2b. Furthermore, the third carrier gas 3c introduced into the mixing chamber 230 helps the movement of the first metal oxide precursor 2a and the second metal oxide precursor 2b within the mixing chamber 230. I can.

2A, 8, and 9A, a micronozzle 220 connected to the lower end of the mixing chamber 230 is a mixture of the introduced first metal oxide precursor 2a and the second metal oxide precursor 2b. ) Can be sprayed onto the substrate 1 (S320). Subsequently, a composite metal oxide precursor layer may be formed from the mixture sprayed on the substrate 1 (S330).

The mixture of the first metal oxide precursor 2a and the second metal oxide precursor 2b may move to the micro nozzle 220 along the mixing chamber 230 by the third carrier gas 3c. Subsequently, the mixture may be jet sprayed onto the substrate 1 through the micro nozzle 220 by the third carrier gas 3c. By using the third carrier gas 3c, the injection speed and the injection amount of the injected mixture may be adjusted. The micro nozzle 220 may include a third heater (not shown), and condensation of the mixture in the micro nozzle 220 may be prevented by using the third heater.

The mixture sprayed from the micro nozzle 220 may be cooled and condensed to form the composite metal oxide precursor layer. For example, the composite metal oxide precursor layer may be a zinc-indium acetylacetonate layer. The zinc-indium acetylacetonate layer is not simply in a state in which zinc acetylacetonate and indium acetylacetonate are mixed, but may exist as a compound through a chemical bond. This is because, as the mixture is condensed from high temperature to low temperature, or through a post-treatment process, chemical reactions may additionally occur with each other.

2A, 8, 9A, and 9B, the composite metal oxide layer 14 may be formed by irradiating an electromagnetic wave to the composite metal oxide precursor layer (S340). When electromagnetic waves are irradiated to the composite metal oxide precursor layer, the composite metal oxide layer 14 may be formed while C and H inside the composite metal oxide precursor layer are separated. For example, when the composite metal oxide precursor layer is a zinc-indium acetylacetonate layer, the zinc-indium acetylacetonate layer may be irradiated with ultraviolet rays to form an indium zinc oxide (InZn _x O _y ) layer. The electromagnetic wave may include at least one of ultraviolet rays, infrared rays, visible rays, microwaves, gamma rays, and X-rays. It can be appropriately selected and used.

In the composite metal oxide layer 14, a composition ratio between the first metal and the second metal constituting the composite metal oxide layer 14 may be determined by the composition of the sprayed mixture. Further, as described above, the composition of the mixture may be determined according to the amount of the first metal oxide precursor 2a introduced into the mixing chamber 230 and the amount of the second metal oxide precursor 2b introduced into the mixing chamber 230. Accordingly, in the method of forming a metal oxide thin film according to the present invention, the composition of the composite metal oxide layer 14 can be easily adjusted by controlling the flow rate of the carrier gas or controlling the sublimation conditions of the metal oxide precursors 2a and 2b.

When the composition ratio of the composite metal oxide layer 14 is changed, its electrical characteristics may be changed. For example, when an oxide layer having high resistance is to be formed on a semiconductor device, the composite metal oxide layer 14 having high resistance may be formed by changing the composition ratio. On the other hand, when it is necessary to form an oxide layer having a small provision such as an electrode, the composite metal oxide layer 14 having a small resistance may be formed by changing the composition ratio. Furthermore, as described above, the composite metal oxide layers 14 having different electrical characteristics may be formed in one process.

Further, referring to FIGS. 2B and 8, the substrate 1 may be a flexible substrate. When the substrate 1 is a flexible substrate, the method of forming a metal oxide thin film according to the present invention may be applied to a roll-to-roll process. This is the same as the method of forming a metal oxide thin film according to an embodiment of the present invention described above with reference to FIGS. 1C and 3.

10A to 10C are cross-sectional views illustrating a method of manufacturing a thin film transistor according to an embodiment of the present invention. As an example, the thin film transistor may be manufactured using the thin film printing apparatus according to an embodiment of the present invention shown in FIG. 1A.

Referring to FIG. 10A, a gate electrode 5 may be formed on the substrate 1. The gate electrode 5 may be formed by depositing a first conductive film on the upper surface of the substrate 1 and then selectively patterning the first conductive film. The first conductive layer is aluminum (Al), aluminum alloy, tungsten (W), copper (Cu), nickel (Ni), chromium (Cr), molybdenum (Mo), titanium (Ti), platinum (Pt). ), and a low resistance opaque conductive material such as tantalum (Ta). The first conductive layer may include an opaque conductive material such as indium-tin-oxide (ITO) and indium zinc oxide (IZO). The first conductive layer may have a multilayer structure in which the low-resistance opaque conductive material and the opaque conductive material are sequentially stacked.

A gate insulating layer 6 may be formed on the gate electrode 5. Specifically, on the substrate 1 on which the gate electrode 5 is formed _{, an inorganic insulating film such as a silicon nitride film (SiN x} ) or a silicon oxide film (SiO ₂ ), or a high dielectric property such as a hafnium (Hf) oxide film and an aluminum oxide film A gate insulating film 6 including an oxide film may be formed. The gate insulating layer 6 may be formed to completely cover the gate electrode 5, and thus the gate electrode 5 may be positioned between the gate insulating layer 6 and the substrate 1. Although not particularly limited, the gate insulating film 6 may be formed using chemical vapor deposition (CVD) or plasma enhanced chemical vapor deposition (PECVD).

Referring to FIG. 10B, a metal oxide thin film 4 may be formed on the gate insulating layer 6. The metal oxide thin film 4 is an active layer, and may be, for example, an amorphous zinc oxide semiconductor layer.

The metal oxide thin film 4 may be formed according to the method of forming a metal oxide thin film according to an embodiment of the present invention described above with reference to FIGS. 1A and 3. Referring to FIGS. 1A, 3 and 10B, the method of forming the metal oxide thin film includes vaporizing the first metal oxide precursor 2 (S100), and the vaporized first metal oxide precursor 2 Introducing into the mixing chamber 130 using the first carrier gas 3 (S110), the micronozzle 120 connected to the lower end of the mixing chamber 130 with the introduced first metal oxide precursor 2 Spraying onto the gate insulating film 6 through (S120), and forming a first metal oxide precursor layer from the first metal oxide precursor 2 spraying onto the gate insulating film 6 (S130) , Forming the first metal oxide layer 4 by irradiating electromagnetic waves to the first metal oxide precursor layer (S140). Here, the first metal oxide precursor 2 may be zinc acetylacetonate, and the first metal oxide layer 4 may be the metal oxide thin film 4 and may be a zinc oxide (ZnO) layer. S100 to S140 are the same as described above in an embodiment of the present invention.

As another example, the metal oxide thin film 4 may be formed according to the method of forming a metal oxide thin film according to another embodiment of the present invention described above with reference to FIGS. 2A and 8. That is, the metal oxide thin film 4 may be a composite metal oxide layer. Here, the first metal oxide precursor 2 may be zinc acetylacetonate, and the second metal oxide precursor may be indium acetylacetonate. The composite metal oxide layer may be an amorphous zinc oxide-based composite semiconductor layer, and specifically, may be an indium zinc oxide (InZn _x O _y ) layer.

The metal oxide thin film 4 may be a pattern formed only on a partial region of the gate insulating film 6. Specifically, from a plan view, the metal oxide thin film 4 may be a pattern that may overlap the gate electrode 5. According to an embodiment of the present invention, a pattern of the metal oxide thin film 4 may be formed by using the method of forming the predetermined pattern 4'P described above with reference to FIGS. 4A to 4C. Therefore, the pattern can be formed without a separate patterning process for the metal oxide thin film 4.

Referring to FIG. 10C, a source electrode 7 and a drain electrode 8 may be formed on the metal oxide thin film 4. The source electrode 7 and the drain electrode 8 may be formed by depositing a second conductive layer on the metal oxide thin film 4 and the exposed gate insulating layer 6 and then selectively patterning the second conductive layer. The second conductive layer may be formed to completely cover the upper surface of the metal oxide thin film 4 and the exposed upper surface of the gate insulating layer 6. In this case, the source electrode 7 and the drain electrode 8 may be simultaneously formed from the second conductive layer.

The second conductive layer is aluminum (Al), aluminum alloy, tungsten (W), copper (Cu), nickel (Ni), chromium (Cr), molybdenum (Mo), titanium (Ti), platinum (Pt). ), and a low resistance opaque conductive material such as tantalum (Ta). The second conductive layer may include an opaque conductive material such as indium-tin-oxide (ITO) and indium zinc oxide (IZO). The second conductive layer may have a multilayer structure in which the low-resistance opaque conductive material and the opaque conductive material are sequentially stacked.

The source electrode 7 and the drain electrode 8 exist on the same layer, but may be spaced apart from each other. Further, the source electrode 7 and the drain electrode 8 may be electrically connected to the metal oxide thin film 4.

A thin film transistor may be provided through the method of manufacturing a thin film transistor according to an embodiment of the present invention described with reference to FIGS. 10A to 10C. Although not additionally shown, a contact electrically connected to the source electrode 7 and the drain electrode 8 may be formed thereafter, and a protective layer capable of protecting the thin film transistor may be formed.

< Experimental example 1>

A metal oxide thin film was prepared according to the method of forming a metal oxide thin film according to the present invention, and characteristics thereof were examined as follows.

Zinc acetylacetonate, which is an organometallic compound, as a metal oxide precursor was introduced into a storage chamber in a metal oxide thin film printing apparatus. After heating the storage chamber to vaporize the zinc acetylacetonate, it was sprayed onto the substrate. At this time, helium was used as a carrier gas. After spraying, a zinc acetylacetonate layer was formed on the substrate (Comparative Example 1).

Heat treatment was performed while irradiating ultraviolet rays to the zinc acetylacetonate layer. The ultraviolet light had a wavelength of 250 nm, and it was irradiated for several minutes in the atmosphere. At this time, the temperature of the substrate was maintained at 200°C. Thus, a zinc oxide layer was formed from the zinc acetylacetonate layer (Example 1).

The experiment was conducted as follows for Comparative Example 1 in which zinc acetylacetonate was sprayed and deposited, and for Example 1 in which ultraviolet rays and heat treatment were additionally performed in Comparative Example 1.

First, the refractive indexes of the thin film of Comparative Example 1 and the thin film of Example 1 were measured and shown in FIG. 11. Sample 1 of FIG. 11 shows Comparative Example 1, and Sample 5 shows Example 1. In addition, Samples 2 to 4 of FIG. 11 are samples obtained by sequentially varying degrees of UV and heat treatment in Comparative Example 1.

11, Comparative Example 1 (Sample 1) has a refractive index of about 1.30, it can be confirmed that the carbon component is contained. On the other hand, Example 1 (Sample 5) has a refractive index of about 2.01, it can be confirmed that it is almost identical to the refractive index of the zinc oxide.

X-ray diffraction analysis was performed on each of the thin film of Comparative Example 1 and the thin film of Example 1, and the results are shown in FIG. 12.

As shown in FIG. 12, the thin film of Comparative Example 1 (As-dep) did not show special crystallinity, but the thin film of Example 1 (ZnO) exhibited a diffraction pattern of zinc oxide.

The electrical properties of the thin film of Example 1 were analyzed, and the results are shown in FIG. 13.

As shown in FIG. 13, it can be seen that the IV curve of the thin film of Example 1 exhibits n-type semiconductor characteristics.

Through the above experiments, it can be seen that the method of forming a metal oxide thin film according to the present invention can effectively convert a metal oxide precursor into a metal oxide through electromagnetic wave irradiation. In addition, it can be seen that the metal oxide thin film according to the present invention can have semiconductor properties, and thus can be applied as an active layer of a thin film transistor.

Claims (20)

Vaporizing the first metal oxide precursor;
Introducing the vaporized first metal oxide precursor into a mixing chamber using a first carrier gas;
Spraying the introduced first metal oxide precursor onto a substrate through a micronozzle connected to a lower end of the mixing chamber to form a first metal oxide precursor layer on the substrate; And
A method of forming a metal oxide thin film comprising forming a first metal oxide layer by irradiating an electromagnetic wave to the first metal oxide precursor layer.
The method of claim 1,
The first metal oxide precursor is an organometallic compound capable of vaporizing at a higher pressure and lower temperature than the first metal oxide containing the same metal element as the first metal oxide precursor.
The method of claim 1,
Vaporizing the first metal oxide precursor,
A method of forming a metal oxide thin film, comprising vaporizing the first metal oxide precursor in the absence of a solvent.
The method of claim 1,
Forming the first metal oxide precursor layer:
Spraying the introduced first metal oxide precursor to a first region on the substrate to form the first metal oxide precursor layer on the first region; And
Injecting the introduced first metal oxide precursor to a second region adjacent to the first region to form a predetermined pattern,
The predetermined pattern is a method of forming a metal oxide thin film including a first metal oxide precursor layer on the first region and a first metal oxide precursor layer on the second region connected thereto.
The method of claim 1,
The method of forming a metal oxide thin film in which the amount of the first metal oxide precursor introduced into the mixing chamber is controlled by the flow rate of the first carrier gas.
The method of claim 1,
Vaporizing the second metal oxide precursor;
Introducing the vaporized second metal oxide precursor into a mixing chamber using a second carrier gas;
The introduced second metal oxide precursor is sprayed onto the substrate through a micronozzle connected to the lower end of the mixing chamber to form a second metal oxide precursor layer on the first metal oxide precursor layer or the first metal oxide layer. To do; And
The method of forming a metal oxide thin film further comprising forming a second metal oxide layer by irradiating an electromagnetic wave to the second metal oxide precursor layer.
The method of claim 6,
The method of forming a metal oxide thin film in which the first metal oxide layer formed using the first metal oxide precursor layer and the second metal oxide layer formed using the second metal oxide precursor layer are sequentially stacked.
The method of claim 1,
The electromagnetic wave irradiation is performed at the same time as the formation of the first metal oxide precursor layer or after the formation of the first metal oxide precursor layer.
The method of claim 1,
Forming the first metal oxide layer,
And converting the partial region of the first metal oxide precursor layer into the first metal oxide layer by irradiating an electromagnetic wave to a partial region of the first metal oxide precursor layer.
The method of claim 1, wherein the electromagnetic wave includes at least one of ultraviolet rays, infrared rays, visible rays, microwaves, gamma rays, and X rays.
The method of claim 1, wherein forming the first metal oxide layer,
A method of forming a metal oxide thin film further comprising performing a post heat treatment after irradiation of electromagnetic waves.
Vaporizing the first metal oxide precursor and the second metal oxide precursor, respectively;
The vaporized first metal oxide precursor and the vaporized second metal oxide precursor are introduced into a mixing chamber using a first carrier gas and a second carrier gas, respectively, so that the first metal oxide precursor and the second metal oxide precursor are Forming a mixture;
Spraying the mixture onto a substrate through a micro nozzle connected to a lower end of the mixing chamber to form a composite metal oxide precursor layer on the substrate; And
A method of forming a metal oxide thin film comprising forming a composite metal oxide layer by irradiating an electromagnetic wave to the composite metal oxide precursor layer.
The method of claim 12, wherein the amount of the first metal oxide precursor and the amount of the second metal oxide precursor introduced into the mixing chamber are respectively controlled by a flow rate of the first carrier gas and a flow rate of the second carrier gas, ,
The composition of the composite metal oxide layer is controlled by the amount of the first metal oxide precursor and the amount of the second metal oxide precursor introduced into the mixing chamber.
A first storage chamber containing a first metal oxide precursor and having a first heater for vaporizing the first metal oxide precursor;
A mixing chamber connected to the first storage chamber, wherein the vaporized first metal oxide precursor is introduced together with a first carrier gas, and the first metal oxide precursor and the first carrier gas move to a micro nozzle connected to the lower end ;
A first carrier gas valve controlling an amount of the first metal oxide precursor introduced into the mixing chamber;
A micro nozzle spraying the first metal oxide precursor;
A first electromagnetic wave irradiator for irradiating electromagnetic waves;
A first stage in which a substrate is loaded and a first metal oxide precursor layer is formed on the substrate; And
Including a second stage for loading the substrate moved from the first stage,
The first electromagnetic wave irradiator is a metal oxide thin film printing apparatus for converting the first metal oxide precursor layer into a first metal oxide layer by irradiating the electromagnetic wave onto the substrate loaded in the second stage.
The method of claim 14,
The substrate is a flexible substrate,
The flexible substrate is a metal oxide thin film printing apparatus that moves from the first stage to the second stage by a roll.
The method of claim 14,
Metal oxide thin film printing apparatus further comprising a deposition chamber including the first storage chamber, the mixing chamber, the micro nozzle, the first electromagnetic wave irradiator, the first stage and the second stage therein.
The method of claim 14,
On the second stage, the metal oxide thin film printing apparatus further comprising a second electromagnetic wave irradiator for irradiating an electromagnetic wave for selectively heating the first metal oxide precursor layer or the first metal oxide layer.
The method of claim 14,
A second storage chamber containing a second metal oxide precursor and having a second heater for vaporizing the second metal oxide precursor; And
Further comprising a second carrier gas valve for adjusting the amount of the second metal oxide precursor introduced into the mixing chamber,
The mixing chamber is connected to the second storage chamber, and the vaporized second metal oxide precursor is introduced together with a second carrier gas,
The micro nozzle is a metal oxide thin film printing apparatus for spraying a first metal oxide precursor, a second metal oxide precursor, or a mixture thereof.
The method of claim 18,
In the mixing chamber, the first metal oxide precursor and the second metal oxide precursor are mixed,
The micro nozzle is a metal oxide thin film printing apparatus for spraying a mixture of the first metal oxide precursor and the second metal oxide precursor.
The method of claim 18,
Metal oxide thin film printing apparatus further comprising a controller for individually controlling the first carrier gas valve and the second carrier gas valve.

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