KR20140066897A - Apparatus for forming organic thin film and manufacturing of organic solar cell and oled - Google Patents

Abstract

An apparatus for forming an organic thin film of the present invention forms at least one of an organic light emitting layer (a photoactive layer) and an electron transport layer on a substrate when forming an OLED or an organic solar cell. The organic thin film forming apparatus comprises: a spray unit for forming an organic thin film by spraying a solution on the surface of a substrate; and a hot gas spraying unit for volatilizing solvent contained in the solution by spraying the hot gas to the solution which is flying by being sprayed from the spray unit. Surface roughness of the organic thin film applied to the substrate can be precisely formed by volatilizing the solvent by spraying the hot gas when the solution is flying after being sprayed from a nozzle. The manufacturing process and the production cost can be reduced since an additional heat treatment apparatus for volatilizing the solvent is not required.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an organic thin film forming apparatus for forming an organic thin film for OLED and an organic solar cell,

The present invention relates to an organic thin film forming apparatus and an organic thin film forming method for forming an organic thin film on a substrate when manufacturing organic light emitting diodes (OLED) and organic solar cells, and more particularly, An organic thin film forming apparatus for forming an organic thin film having a uniform thickness on a flexible substrate or a substrate having three-dimensional curvature by using the organic thin film and improving the precision of the surface roughness of the organic thin film, And a method of manufacturing an organic solar cell.

In general, OLEDs (Organic Light Emitting Diodes) have advantages such as low power consumption, fast response speed and wide viewing angle. These OLEDs are simple and easy to fabricate, so they are used in ultra-thin and light-weight display devices with a thickness of less than 1 mm. Furthermore, they are manufactured on flexible substrates such as plastic instead of glass substrates to produce thinner, lighter, ) Devices.

Such an OLED is formed of a multilayer organic thin film such as an anode electrode, a hole transporting layer, an organic light emitting layer, an electron transporting layer, an electron injecting layer, and a cathode.

The organic solar cell is formed of a multilayer organic thin film such as an anode electrode, a hole transporting layer, a photoactive layer, an electron transporting layer, an electron injecting layer, and a cathode.

OLEDs and organic solar cells having such a structure are widely known as vacuum evaporation methods for forming organic thin films such as a hole transport layer, an organic light emitting layer (photoactive layer), an electron injection layer, and an electron transport layer.

When the organic thin film is manufactured through such a sputtering or vacuum deposition process, a vacuum chamber is required, and the manufacturing process is complicated, the cost is very high, the mass production is difficult, the production of flexible OLED is not suitable, have.

In the case of the electron injection layer, a super-organic thin film of about 1 nm or less made of LiF, CsF, NaF or Cs 2 CO 3 is formed by vapor deposition, or a layer of about 20 nm or so made of Ca, Li, Ba, Cs or Mg is used as an electron injection layer Such a layer is very vulnerable to oxygen and moisture in the outside air even when the cathode is further deposited, which has a great problem of shortening the lifetime of the device, and these materials are not easily handled in the process.

In addition, since the organic thin film having a thickness of 0.5 to 2 nm is used in the structure of LiF / Al, which is the most commonly used electron injection layer / cathode structure, in the case of the super-organic thin film electron injection layer, The surface state of the coating film on the lower layer is very important.

Therefore, it is very difficult to apply the ultra-organic thin film electron injection layer to a solution process because it is not easy to have sufficient coating performance in a solution process such as roll-to-roll printing, inkjet printing, screen printing, spray coating or dip coating.

In order to solve such a problem, development of an organic thin film forming apparatus using a spray method in which an organic thin film is formed by spraying a solution onto a substrate by a spraying method is actively under development.

As a method for manufacturing an organic thin film transistor using a conventional spray method, there is a method of preparing an organic thin film transistor by preparing a substrate, preparing a solution to be applied to the substrate, as disclosed in Patent Registration No. 10-1172187 (Aug. 27, 2012) A shadow mask having a pattern formed on the substrate; a step of applying the prepared solution to a shadow mask through a spray device; and a heat treatment after the application step is completed And evaporating the remaining solvent.

Since the organic thin film transistor using the conventional spray method uses a spray method, a uniform organic thin film can be formed. However, after the solution is coated on the substrate, the solvent contained in the solution is evaporated through a separate heat treatment A separate heat treatment apparatus and a heat treatment process are required, which complicates the manufacturing process, increases the manufacturing cost, and performs heat treatment in a state where the solution is coated on the substrate, so that the solvent is evaporated and the surface roughness of the organic thin film is deteriorated there is a problem.

Patent Registration No. 10-1172187 (Aug. 27, 2012)

Accordingly, it is an object of the present invention to provide a method of forming an organic thin film by spraying a solution by spraying and volatilizing a solvent by spraying a high-temperature gas while the solution is flying to thin an organic thin film, An OLED capable of forming an organic thin film of uniform thickness on the surface of a flexible substrate and a substrate having three-dimensional curvature, and an organic thin film forming apparatus for manufacturing an organic solar cell, and an OLED and an organic solar cell manufacturing method using the apparatus .

Another object of the present invention is to improve the precision of the surface roughness of the organic thin film applied to the substrate by spraying the high temperature gas and volatilizing the solvent while the solution is sprayed from the nozzle and flying in the nozzle, An organic thin film forming apparatus for organic solar cell fabrication, an OLED using the organic thin film forming apparatus, and a method for manufacturing an organic solar cell.

Another object of the present invention is to provide a flexible substrate which is capable of volatilizing most of the solvent contained in the solution by spraying a high temperature gas onto the solution while the solution is in flight so that the substrate can be heated to a low temperature even when the substrate is heated, An OLED capable of manufacturing flexible OLEDs and organic solar cells, an organic thin film forming apparatus for manufacturing organic solar cells, an OLED, and a method for manufacturing an organic solar cell.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. .

In order to attain the above object, the organic thin film forming apparatus of the present invention forms at least one of an organic light emitting layer (photoactive layer) and an electron transporting layer on a substrate when an OLED or an organic solar cell is manufactured, And a high temperature gas injection unit for spraying hot gas from the spray unit to the solution in flight to volatilize the solvent contained in the solution.

The spray unit of the present invention includes a supply unit connected to a storage tank in which a solution is stored to supply a solution, and a spray nozzle mounted on a lower side of the supply unit to spray the solution onto the surface of the substrate. The spray unit includes an air spray system, Either the air spray method or the hybrid spray method using the electric spray method can be used.

The high temperature gas injection unit according to the present invention comprises a housing mounted on an outer surface of an injection nozzle and having a space portion into which a high temperature gas flows and having a spray passage for spraying a high temperature gas on a lower side, And a heating unit installed on the pipe and heating the gas supplied to the body.

The apparatus for forming an organic thin film according to the present invention further includes a control unit for controlling the pressure and the temperature of the gas of the high temperature gas injection unit, wherein the control unit includes an input unit for inputting a temperature and a pressure by a user's operation, A control unit for controlling a heating unit for heating the gas based on the data input from the input unit, a temperature sensor and a pressure sensor, and a pressure control unit for controlling the pressure of the gas, .

The OLED and organic solar cell manufacturing method of the present invention includes the steps of preparing a transparent and flexible substrate, forming an anode electrode on the substrate, forming a hole transporting layer on the anode electrode, Forming an electron transporting layer on the organic light emitting layer or the photoactive layer; forming an electron injection layer on the electron transporting layer; forming a cathode electrode Wherein at least one of the step of forming the hole transporting layer, the step of forming the organic light emitting layer and the photoactive layer is formed by a spraying method, and the spraying method is a method in which the pressure of the gas And setting the temperature; spraying the solution in the spray unit; Volatilizing the solvent contained in the solution by spraying a high temperature gas onto the solution in flight, and spraying the solution onto the surface of the substrate to form an organic thin film.

As described above, the organic thin film forming apparatus and the organic thin film forming method for manufacturing an OLED and an organic solar battery of the present invention spray a solution by a spray method, spray a high temperature gas to a solution when the solution is sprayed from the spray nozzle, The thickness of the organic thin film can be reduced and the thickness of the organic thin film can be controlled. In particular, the organic thin film having the uniform thickness can be formed on the surface of the flexible substrate and the substrate having the three-dimensional curvature.

In addition, the organic thin film forming apparatus and the organic thin film forming method for manufacturing an organic light emitting diode (OLED) and organic solar cell of the present invention are characterized in that when the solution is sprayed from a nozzle and a high temperature gas is sprayed while the solution is sprayed, the solvent is volatilized, The precision can be improved and a separate heat treatment step for volatilizing the solvent is not required, so that the manufacturing process can be shortened.

In addition, the organic thin film forming apparatus and the organic thin film forming method for manufacturing an organic light emitting diode (OLED) and organic solar cell of the present invention can emit a hot gas into a solution to volatilize most of the solvent contained in the solution, Even if the substrate is heated, the substrate can be heated at a low temperature, so that a flexible substrate can be used, which is advantageous in manufacturing a flexible OLED and an organic solar cell.

1 is a configuration diagram of an organic thin film forming apparatus according to an embodiment of the present invention.
2 is a cross-sectional view of an organic thin film forming apparatus according to an embodiment of the present invention.
3 is a block diagram of a control unit for controlling an organic thin film forming apparatus according to an embodiment of the present invention.
4 is a flow chart showing a process of manufacturing an organic solar battery according to an embodiment of the present invention.
5 is a process flow diagram illustrating an OLED manufacturing process according to an embodiment of the present invention.
6 is a flow chart illustrating a method of forming an organic thin film according to an embodiment of the present invention.
7 is a photograph showing the organic thin film produced by Example 1. Fig.
8 is a photograph showing the organic thin film produced in Example 2. Fig.
9 is a photograph showing the organic thin film produced by Example 3. Fig.
10 is a photograph showing the organic thin film produced by Example 4. FIG.
11 and 12 are enlarged photographs of the surface of the thin film produced by the organic thin film forming apparatus of the present invention and the thin film produced by the conventional spray method.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The sizes and shapes of the components shown in the drawings may be exaggerated for clarity and convenience. In addition, terms defined in consideration of the configuration and operation of the present invention may be changed according to the intention or custom of the user, the operator. Definitions of these terms should be based on the content of this specification.

2 is a cross-sectional view of an organic thin film forming apparatus using a spray method according to an embodiment of the present invention. Referring to FIG.

1 and 2, an apparatus for forming an organic thin film according to an embodiment of the present invention is for manufacturing an organic light emitting diode (OLED) and an organic solar cell. The organic thin film forming apparatus includes a spray Unit 20 and a high-temperature gas injection unit 30 for spraying a high-temperature gas into the solution in the air sprayed from the spray unit 20 to volatilize the solvent contained in the solution.

The OLED is formed of a multilayer organic thin film such as an anode electrode, a hole transporting layer, an organic light emitting layer, an electron transporting layer, an electron injecting layer and a cathode, and the organic solar cell includes an anode electrode, a hole transporting layer, An electron transport layer, an electron injection layer, and a cathode.

An apparatus for forming an organic thin film according to one embodiment is an apparatus for forming an organic thin film such as a hole transport layer, an organic light emitting layer (photoactive layer), an electron injection layer, and an electron transport layer on a substrate when an OLED and an organic solar battery are manufactured.

The spray unit 20 is disposed at a certain distance from the upper surface of the substrate 10 so that the solution sprayed from the spray unit 20 is uniformly distributed on the surface of the substrate 10. [ Then, the movable unit 12 can be moved in the left-right direction, the right-left direction, and the back-and-forth direction on the upper surface of the substrate 10.

The substrate can be a variety of substrates such as a substrate having a flat surface, a substrate having a three-dimensional curvature, a flexible substrate, or a substrate relatively weak in heat.

The substrate 10 may be provided with a heating unit for heating the substrate 10 to volatilize the solvent remaining in the solution. That is, the solvent contained in the solution is firstly volatilized by the high-temperature gas injection unit 30, and the remaining solvent that has not been volatilized by the high-temperature gas injection unit 30 is heated by the heating unit provided on the substrate 10 ) Is heated and finally volatilized.

Since most of the solvent is volatilized by the high temperature gas injection unit, the amount of the solvent contained in the solution applied to the substrate is very small, so that the heating temperature of the substrate 10 does not need to be high. Therefore, in this embodiment, since the substrate heating temperature is relatively low, a substrate that is weak against heat can be used.

Here, the heating temperature of the substrate 10 is preferably set to 70 to 180 占 폚.

The spray unit 20 includes a supply unit 24 connected to the storage tank 22 for supplying the solution and a spray nozzle mounted on the lower side of the supply unit 24 for spraying the solution onto the surface of the substrate 10 26).

Here, the spray unit 20 can be any of an air spray method, an electric spray method, or a hybrid spray method combining an air spray method and an electric spray method.

The solution may be an organic material, a polymer, an inorganic material, a metal-based organic polymer capable of forming an organic thin film, and a mixture of one or more kinds thereof. The solvent may be a solvent A solvent having volatility such as water, benzene series, alcohol series, and chloroform may be used.

The upper end of the supply part 24 is connected to the reservoir tank 22 and the lower end of the supply part 24 is sealingly connected to the injection nozzle 26. A positive terminal 52 connected to the high voltage generating part 50 is installed on one side of the supplying part 24 to charge the solution when the electric spraying method is used.

That is, in the case of the electric spraying method, a high voltage is applied between the spray unit 20 and the substrate 10 by the high-voltage generating unit 50 so that the solution is sprayed from the spray unit 20 to be coated on the surface of the substrate 10 .

The lower end of the spray nozzle 26 is formed to have a smaller inner diameter as it goes downward. At the end of the spray nozzle 26, a conductive nozzle tip 28 for charging a coating solution is provided.

Here, the voltage applied between the spray unit and the substrate is 8 to 14 kV, the distance between the spray nozzle and the substrate is 6 to 12 cm, and the solution discharge amount is 40 to 1000ul / min.

The high temperature gas injection unit 30 includes a housing 34 provided on the outer surface of the injection nozzle 26 and having a space portion 32 into which hot gas flows and a spray passage 36 through which a hot gas is sprayed on the lower side, A pipe 40 connected to one side of the housing 34 for introducing the gas into the space 32 of the housing and a heating unit 42 for heating the gas passing through the pipe 40 ).

Any structure can be applied as long as the heating unit 42 can heat the gas passing through the pipe 40. As the gas heating method, any of the heating method by conduction, the heating method by convection, and the heating method by radiation can be applied.

For example, the heating unit 42 may include a heating coil arranged to be wrapped around an outer circumferential surface of the pipe 40, and a method of heating the gas passing through the pipe by applying power to the heating coil may be applied.

The pipe 40 is connected to the gas storage tank in which the gas is stored, and is provided with a pressure regulating unit 44 for regulating the injection pressure of the gas stored in the gas storage tank.

Here, the gas may be air, nitrogen, an oxygen inert gas, or a mixed gas of at least two mixed gases.

The housing 34 is fixed to the outer surface of the injection nozzle 26 with a predetermined gap so that a space is formed between the inner surface of the housing and the outer surface of the injection nozzle 26. Therefore, the hot gas introduced into the space portion comes into direct contact with the outer surface of the injection nozzle 26, thereby heating the solution passing through the injection nozzle 26.

As described above, by heating the solution passing through the injection nozzle 26 by the high-temperature gas injection unit 30, it is possible to maintain a suitable viscosity for spraying the solution, thereby improving the spraying performance of the solution.

A seal ring 46 is mounted on one side of the housing 34 mounted to the spray nozzle 26 to maintain airtightness between the housing and the spray nozzle 26.

The end of the injection nozzle 26 is formed so as to pass through the center of the injection path 36 formed on the lower side of the housing 34 so that the high temperature gas is sprayed while the injection nozzle is wrapped. Therefore, since the hot gas is injected in a form to surround the outside of the solution injected from the injection nozzle, the solvent contained in the solution can be precisely volatilized.

Then, the hot gas is injected in the same direction as the spraying direction of the spraying nozzle 26, so that the solution can be imparted with a straightness, thereby preventing the solution from being blown and spraying the solution to the precise position of the substrate , The thickness of the organic thin film can be more uniformly formed.

The pressure of the gas is preferably 0.04 to 0.12 MPa and the gas temperature is preferably set to about 80 to 150 DEG C. [

Here, if the gas pressure is 0.06 MPa or less, the gas pressure is too low to volatilize the solvent, and if the gas pressure is 0.12 MPa or more, the gas pressure is too high to prevent the solvent from being sprayed onto the substrate. When the gas temperature is lower than 80 캜, the solvent is not volatilized. When the gas temperature is higher than 150 캜, the solute is damaged.

3 is a block diagram of a control unit for controlling an organic thin film forming apparatus according to an embodiment of the present invention.

The control unit includes an input unit 66 for inputting the temperature of the gas and the injection pressure by the user, a temperature sensor 62 installed at one side of the housing 34 for measuring the temperature of the gas flowing into the housing 34, A temperature sensor 62 and a pressure sensor 64 for receiving a signal from the temperature sensor 62 and the pressure sensor 64, And a control unit 60 for controlling the unit 42 and the pressure regulating unit 44. [

When the user inputs the optimum temperature and pressure suitable for volatilizing the solvent according to the type or nature of the solvent contained in the solution, the control unit 60 sets the inputted temperature and pressure as the reference value.

The control unit 60 compares the temperature and the pressure applied from the temperature sensor 62 and the pressure sensor 64 with the reference value and controls the heating unit 42 and the pressure control unit 62 so that the temperature and pressure of the gas can be maintained within the reference value range. And controls the unit 44.

The organic solar cell and the OLED manufacturing process of the present invention thus constructed will be described below.

4 is a process flow diagram illustrating a method of fabricating an organic solar cell according to an embodiment of the present invention.

An organic solar cell manufacturing method will be described below.

First, a substrate is prepared (S110). The substrate is a flexible, flexible, and three-dimensional substrate having a plurality of projections and depressions, and a transparent polymer film is used so that light can be transmitted.

Then, an anode is formed on the surface of the substrate (S120). The anode is formed of a light transmitting material so that light can be transmitted, and a conductive metal material such as a metal oxide such as ITO is used. A screen printing method, a sputtering method, a vacuum deposition method, or the like can be used.

Conductive polymeric materials include PEDOT: PSS (dimethyl sulfoxide), PC (polycarbonates), DMF (dimethyl formamide), HMPA (hexamethyl phosphorotriamide), THF (tetrahydrofuran), EG (ethylene glycol), and NMP (N-methyl-2-pyrrolidone).

Then, a hole transport layer is formed on the anode (S130). Here, the hole transporting layer is formed by the organic thin film forming method using the organic thin film forming apparatus described above.

That is, when the solution forming the hole transporting layer is sprayed by the spray unit and the solvent is volatilized by injecting the high temperature gas into the solution flying the hot gas in the hot gas injection unit, the organic thin film, To form a hole transporting layer. Here, the thickness of the hole transporting layer is preferably set to 50 to 150 nm.

Then, annealing is performed to volatilize the solvent remaining in the applied organic thin film without being removed by the hot gas injection unit. Here, annealing is preferably carried out at 130 DEG C for about 10 minutes.

Then, a photoactive layer is formed on the hole transport layer (S140). Here, the photoactive layer is formed by the organic thin film forming method using the organic thin film forming apparatus described above.

That is, when the solution for forming the photoactive layer is sprayed by the spray unit, and the solvent is volatilized by spraying the high temperature gas onto the solution in the high temperature gas injection unit flying the hot gas, the organic thin film Is applied to form a photoactive layer. Here, the thickness of the photoactive layer is preferably set to 100 to 200 nm.

Then, the photoactive layer is annealed. Here, annealing is preferably carried out at 75 DEG C for 24 hours.

Then, an electron transporting layer is formed in the photoactive layer. (S150) The electron transporting layer may be formed by a vacuum deposition method. Then, an electron injection layer is formed by coating and doping an organic ion material on the electron transport layer (S160).

Finally, when a cathode is formed by depositing a conductive metal on the electron source layer, the manufacture of the organic solar battery is completed (S170).

In the following, an OLED manufacturing process will be described. 5 is a process flow chart showing the OLED manufacturing process of the present invention.

The OLED manufacturing process is the same as the above-described process for manufacturing an organic solar cell, but a process (S140a) for forming an organic light emitting layer is performed instead of the process (S140) for forming an open layer.

Here, the organic light emitting layer is formed by the organic thin film forming method using the organic thin film forming apparatus described above.

That is, when the solution for forming the organic light emitting layer is sprayed by the spray unit, and the solvent is volatilized by spraying the high temperature gas in the solution flying the hot gas in the high temperature gas injection unit, the organic thin film, Thereby forming an organic light emitting layer. Here, the thickness of the hole transporting layer is preferably set to 50 to 150 nm.

At this time, RGB can be separately ejected or mixed by the spray unit.

6 is a flow chart illustrating a method of forming an organic thin film according to an embodiment of the present invention.

The process of forming the organic thin film by the spraying method in manufacturing the organic solar cell and the OLED described above will be described in more detail.

First, the gas pressure and temperature are input (S10). That is, the user inputs the optimal temperature and pressure that can volatilize the solvent depending on the nature of the solution used and the type of solvent. Then, the control unit 60 controls the heating unit 42 to adjust the heating temperature of the gas, and controls the pressure regulating unit 44 to regulate the gas injection pressure.

Here, the pressure of the gas is preferably 0.04 to 0.12 MPa, and the gas temperature is preferably set to 80 to 150 DEG C.

When the pressure and temperature of the gas are completed, the spray unit 20 is operated to spray the solution onto the surface of the substrate 10 (S20). At this time, the substrate 10 may be coated with another layer such as an anode or a hole transport layer.

When the spray unit is an air spray system, air is sprayed to the solution to generate the spray pressure. When the spray unit is an electric spray system, the high voltage generator 50 is turned on to apply a high voltage To inject the solution. In the case of the hybrid method, air is injected, and a high voltage is applied to spray the solution.

Here, the applied voltage between the spray unit and the substrate is set to 8 to 14 kV, the distance between the spray unit and the substrate is 6 to 12 cm, and the discharge amount is set to 40 to 1000ul / min.

As described above, in this embodiment, since the organic thin film is formed by spraying the solution onto the substrate 10 by the spraying method, the thickness of the organic thin film can be made thin and the thickness of the organic thin film can be freely adjusted.

When the solution is sprayed from the spray nozzle 26 before the solution reaches the substrate 10, the high temperature gas is sprayed to the solution to volatilize the solvent contained in the solution (S30).

That is, the heating unit 42 is operated to heat the gas to the set temperature, and the pressure of the gas passing through the pipe 40 by the pressure adjusting unit 44 is adjusted to the set pressure. The hot gas introduced into the housing 34 through the pipe 40 is injected through the injection path 36 to volatilize the solvent contained in the solution in flight.

At this time, when the internal temperature of the housing 34 is measured by the temperature sensor 62 and applied to the control unit 60, the control unit 60 compares the gas temperature applied by the temperature sensor 62 with the reference temperature, And controls the heating unit 42 to maintain the temperature range.

When the pressure of the gas injected from the housing 34 is measured by the pressure sensor 64 and applied to the control unit 60, the control unit 60 compares the gas pressure with the reference pressure, To control the pressure regulating unit (44).

Then, the substrate is heated to a relatively low temperature, and the remaining solvent which can not be removed by the hot gas injection unit is finally volatilized.

Here, since the heating temperature of the substrate is 70-190 ° C, the substrate can be heated at a relatively low temperature. Therefore, it is possible to use various substrates such as a flexible substrate, a weak substrate and a thin substrate, Thereby preventing damage.

In the conventional organic thin film forming apparatus, when the substrate is heated and the solvent is volatilized, the solvent is volatilized in a state of being coated on the substrate. Therefore, the quality of the organic thin film is lowered and the substrate is heated to a temperature at which the solvent can be volatilized. There was this difficult problem.

In this embodiment, since the solvent sprayed from the spray nozzle directly injects the high-temperature gas into the solution in the flying state, the solvent applied to the substrate is substantially eliminated, thereby improving the surface precision of the organic thin film. Quality can be improved.

Further, since it is not necessary to heat the substrate, it is possible to use a substrate which is weak against heat. Even if the substrate is heated to volatilize the solvent remaining in the solution coated on the substrate, since the remaining solvent is volatilized, it is not necessary to set the heating temperature at a high temperature, so that it is possible to use a substrate which is weak against heat.

Example 1

First, Orgacon.TM (Agfa, PEDOT: PSS) was dissolved as 0.8wt% in water as a conductive polymer and filtered with 6um and 0.8um syringe filters to prepare a spray solution. Then, a substrate having a three-dimensional curvature on its surface was prepared.

Nanostructured membranes were prepared by using hybrid spray - type organic thin - film forming apparatus in which the sprayed solution was mixed with electric spraying and air spraying.

That is, it is set so that the applied voltage is 12 kV, the nitrogen pressure is 0.1 Mpa, the distance between the injection nozzle and the substrate is 6 cm, the discharge amount is 700 / / min, the temperature of the substrate is 130 캜 and the gas temperature is 100 캜. A nano organic thin film was formed on the surface of the substrate having three-dimensional curvature by spraying hot gas to the solution in flight in the injection unit.

As shown in the photograph of FIG. 7, when the thickness of the nano organic thin film was measured by scanning electron microscope, the thickness of the top organic thin film was 437 nm, Side) thickness was 421 nm, and the bottom thickness was 433 nm. Thus, the ratio of top / bottom was close to 1 and the ratio of side / bottom was 0.97.

When an organic thin film forming apparatus using the spraying method of the present invention is formed on the surface of a substrate having three-dimensional curvature as in Embodiment 1, an organic thin film having a uniform overall thickness can be obtained and the heating temperature of the substrate can be lowered Can be confirmed.

Example 2

As the OLED light emitting layer, poly (9-vinylcabazole), PBD (2- (4-Biphenylyl) -5-phenyl-1,3,4-oxadiazole), Ir (ppy) ] iridium (III) were mixed in a ratio of 10: 4: 1 and dissolved in monochlorobenzene at a ratio of 0.2 wt% to prepare a spray solution.

The solution thus prepared was filtered using a 6-μm, 0.4-μm syringe filter, and then a nano-envelope was prepared using a hybrid spray-type organic thin-film forming apparatus in which electric spraying and air jetting were mixed.

That is, the spraying unit was sprayed from the spray unit while setting the injection voltage to 10 kV, the nitrogen pressure to 0.06 Mpa, the distance between the injection nozzle and the substrate to 6 cm, the discharge amount to 88 μl / min, the substrate temperature to 130 ° C. and the gas temperature to 100 ° C., The nano organic thin film was formed on the surface of the substrate having three-dimensional curvature by spraying high-temperature gas (100 ° C) onto the solution in flight in the injection unit. Then, the organic thin film sprayed on the substrate was treated with a drying furnace at 75 캜 for 24 hours to perform crosslinking.

As shown in the photograph of FIG. 8, when the thickness of the nano organic thin film was measured by a scanning electron microscope, the thickness of the nano organic thin film was 133 nm, Side) thickness was 117 nm, and the bottom thickness was 123 nm. Thus, the ratio of Top / Bottom was 1.18 and the ratio of Side / Bottom was 0.95.

When an organic thin film forming apparatus using the spraying method of the present invention is formed on the surface of a substrate having a three-dimensional curvature as in Embodiment 2, an organic thin film having a uniform thickness as a whole can be obtained, .

Example 3

The OPV photoactive layer was prepared by mixing PCBM (1- (3-Methoxycarbonyl) -Propyl-1-phenyl = (6,6) C61) with P3HT (Poly (3-hexylthiophene) in a ratio of 1: 1 to obtain monochlorobenzene ) At a ratio of 0.2 wt%, respectively.

The solution thus prepared was filtered using a 6-μm, 0.4-μm syringe filter, and then a nano-envelope was prepared using a hybrid spray-type organic thin-film forming apparatus in which electric spraying and air jetting were mixed.

That is, after setting the applied voltage to 10 kV, the nitrogen pressure to 0.06 Mpa, the distance between the injection nozzle and the substrate to 6 cm, the discharge amount to 350 μl / min, the substrate temperature to 130 ° C. and the gas temperature to 120 ° C., The nano organic thin film was formed on the surface of the substrate having the three-dimensional curvature by spraying hot gas (120 ° C) into the solution flying in the injection unit. Then, the organic thin film sprayed on the substrate was treated with a drying furnace at 75 캜 for 24 hours to perform crosslinking.

As shown in the photograph of FIG. 9, when the thickness of the nano organic thin film was measured by a scanning electron microscope, the thickness of the nano organic thin film was 595 nm, Side) thickness was 560 nm, and the bottom thickness was 551 nm. Therefore, the ratio of the top / bottom was 1.07 and the ratio of the side / bottom was 1.02.

When the organic thin film forming apparatus using the spraying method of the present invention is formed on the surface of the substrate having the three-dimensional curvature as in Embodiment 3, an organic thin film having a uniform thickness as a whole can be obtained, .

Example 4

The OPV photoactive layer was prepared by mixing PCBM (1- (3-Methoxycarbonyl) -Propyl-1-phenyl = (6,6) C61) with P3HT (poly (3-hexylthiophene) in a ratio of 1: 1 and adding chloroform And 0.15 wt%, respectively.

The solution thus prepared was filtered using a 6-μm, 0.4-μm syringe filter, and then a nano-envelope was prepared using a hybrid spray-type organic thin-film forming apparatus in which electric spraying and air jetting were mixed.

That is, the spraying unit is sprayed in the spray unit, and the high-temperature gas is injected from the spray unit at a rate of 10 kV, a nitrogen pressure of 0.06 MPa, a distance of 6 cm between the injection nozzle and the substrate, The nano organic thin film was formed on the surface of the substrate having the three-dimensional curvature by spraying high-temperature gas (90 ° C) into the solution flying in the injection unit. Then, the organic thin film sprayed on the substrate was treated with a drying furnace at 75 캜 for 24 hours to perform crosslinking.

As shown in the photograph of FIG. 10, when the thickness of the nano organic thin film was measured by scanning electron microscope, the thickness of the top organic thin film was 130 nm, Side) thickness was 145 nm, and the bottom thickness was 144 nm. Thus, the ratio of Top / Bottom was 0.90 and the ratio of Side / Bottom was 1.01.

When the organic thin film forming apparatus using the spraying method of the present invention is manufactured on the surface of the substrate having the three-dimensional curvature as in Embodiment 4, an organic thin film having a uniform thickness as a whole can be obtained, .

11 and 12 are enlarged photographs of the surface of the thin film produced by the organic thin film forming apparatus of the present invention and the thin film produced by the conventional spray method.

As shown in FIG. 11, when a thin film is formed by spraying a solution onto the surface of a substrate using a conventional spraying method and the solvent contained in the solution is volatilized by heating the substrate to 200 ° C, State, and heat damage to the solute can be confirmed.

As shown in FIG. 12, when a solvent is volatilized using a high temperature gas, the temperature of the substrate can be relatively low, such as about 130 ° C., so that the surface of the substrate is smoothly formed, .

 While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be construed as limited to the embodiments set forth herein. Various changes and modifications may be made by those skilled in the art.

10: substrate 12: mobile unit
20: Spray unit 22: Storage tank
24: supply part 26: injection nozzle
28: conductor nozzle tip 30: high temperature gas injection unit
32: space part 34: housing
36: injection passage 40: pipe
42: Heating unit 44: Pressure regulating unit
50: high voltage generating unit 60: control unit
62: temperature sensor 64: pressure sensor
66:

Claims (10)

A spray unit that forms an organic thin film by spraying a solution onto a substrate for manufacturing an OLED and an organic solar cell; And
And a high-temperature gas injection unit for injecting a high-temperature gas into the solution injected from the spray unit to volatilize the solvent contained in the solution. The method according to claim 1,
Wherein the spray unit includes a supply unit connected to a storage tank in which a solution is stored to supply a solution, and a spray nozzle mounted on a lower side of the supply unit to spray the solution onto the surface of the substrate,
An organic spraying method, an air spraying method, an electric spraying method, and a hybrid spraying method using an air spraying method and an electric spraying method. 3. The method of claim 2,
Wherein the high temperature gas injection unit is mounted on an outer surface of the injection nozzle and has a space in which a high temperature gas is introduced and in which a spray passage for injecting a high temperature gas is formed, And a heating unit installed on the pipe and heating a gas supplied to the body. The organic thin film forming apparatus for organic solar cell according to claim 1, The method of claim 3,
Wherein the space is formed between the inner surface of the housing and the outer surface of the injection nozzle so that the hot gas introduced into the space of the housing can heat the injection nozzle. The method of claim 3,
Wherein an end of the injection nozzle passes through the center of the injection path formed on the lower side of the housing. The method according to claim 1,
And a control unit for controlling the pressure and the temperature of the gas in the high temperature gas injection unit, wherein the control unit includes an input unit for inputting a temperature and a pressure operated by a user, a temperature sensor for measuring the temperature of the gas, And a control unit for controlling a heating unit for heating the gas based on the data input from the input unit, the temperature sensor and the pressure sensor, and a pressure control unit for controlling the pressure of the gas, And an organic thin film forming apparatus for manufacturing an organic solar cell. Preparing a substrate having a three-dimensional curvature and being transparent and flexible;
Forming an anode electrode on the substrate;
Forming a hole transport layer on the anode electrode;
Forming an organic light emitting layer or a photoactive layer on the hole transporting layer;
Forming an electron transport layer on the organic light emitting layer or the photoactive layer;
Forming an electron injection layer on the electron transport layer; And
And forming a cathode electrode on the electron injecting side. 8. The method of claim 7,
At least one of the steps of forming the hole transport layer, forming the organic light emitting layer, and photoactive layer includes: setting the pressure and temperature of the gas according to the type of the solvent included in the solution;
Spraying a solution in a spray unit;
Volatilizing the solvent contained in the solution by spraying a high temperature gas onto the solution being sprayed and flying in the spray unit; And
And spraying the solution onto the surface of the substrate to form an organic thin film. 8. The method of claim 7,
Wherein the gas pressure is 0.06 to 0.12 MPa and the gas temperature is 80 to 150 ° C. 8. The method of claim 7,
Further comprising the step of spraying the solution onto the substrate and then heating the substrate to volatilize the solvent remaining in the solution,
Wherein the heating temperature of the adhesive sheet is 70 to 190 ° C.

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