KR20130027725A - Organic electronic devices and manufacturing method of the same - Google Patents

Abstract

PURPOSE: An organic electronic device and a manufacturing method thereof are provided to efficiently improve energy conversion efficiency by minimizing an energy barrier between a metal electrode and a photoactive layer. CONSTITUTION: A bottom electrode(200) is formed on a substrate(100). A hole transport layer(300) is formed on the bottom electrode. The hole transport layer includes at least one of graphene oxide and NiOx. A photoactive layer(400) is formed on the hole transport layer. A top electrode(500) is formed on the photoactive layer. A passivation layer(600) is formed on the top electrode.

Description

Organic electronic device and manufacturing method therefor {ORGANIC ELECTRONIC DEVICES AND MANUFACTURING METHOD OF THE SAME}

TECHNICAL FIELD The present invention relates to the field of organic electronic devices, and more particularly, to an organic electronic device and a method of manufacturing the same, which can effectively improve energy conversion efficiency by minimizing an energy barrier between a metal electrode and a photoactive layer.

In general, an organic electronic device has a structure including an organic material layer between an anode and a cathode. In this case, the organic material layer is often made of a multilayer structure composed of different materials to increase the efficiency and stability of the organic electronic device, for example, it may be made of a hole injection layer, a hole transport layer, an organic active layer, an electron transport layer, an electron injection layer.

Materials used as the hole injection layer and the hole transport layer forming the organic material layer in the organic electronic device are mostly thermal deposition, chemical method atomic layer deposition (ALD) and metal organic chemical vapor deposition (MOCVD) It is formed by the method. Among the above-described methods, the atomic layer deposition method or the metal organic chemical vapor deposition method is difficult to use a substrate having a low melting point because the process temperature is relatively high, there is a problem that corrosion of the reactor or the like due to the reaction by-product hydrogen chloride.

In addition, the thermal evaporation method as disclosed in Korean Patent Laid-Open No. 10-2004-0102523 has a problem in that a large area is applied. In addition, metal organic chemical vapor deposition (MOCVD), which is a method of depositing a thin film using a solid or liquid source in the form of a metal organic material, is more difficult to accurately control the thickness of a thin film than the atomic layer deposition method (ALD). There is a problem that the formation temperature of is relatively high and the surface roughness is large.

In addition, the materials used for the electron injection layer and the electron transport layer are various such as sputtering, chemical vapor deposition, metal organic chemical vapor deposition, molecular beam deposition, metal organic molecular beam deposition, pulse laser coating, atomic layer coating, and the like. It is formed by the branch coating method. However, the above-described methods have a problem of expensive equipment, complicated process, and damage to a thin film and a substrate to be deposited when grown at a high temperature.

Therefore, there is a need for a new organic electronic device structure and a method of manufacturing the same that can solve the conventional problems and improve the characteristics of the device.

Korean Patent Publication No. 10-2004-0102523 (published Dec. 8, 2004)

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an organic electronic device and a method for manufacturing the same, which improve the efficiency of the manufacturing process and have excellent characteristics by forming a hole transport layer using a solution process in order to solve the above problems.

An organic electronic device of the present invention for solving the above problems is a substrate; A lower electrode formed on the substrate; A hole transport layer formed on the lower electrode; A photoactive layer formed on the hole transport layer; It comprises an upper electrode formed on the photoactive layer.

In the organic electronic device of the present invention, the hole transport layer, a graphene oxide layer formed on the lower electrode; A NiO x layer formed on the graphene oxide layer; . ≪ / RTI >

In the organic electronic device of the present invention, the hole transport layer, NiOx layer formed on the lower electrode; A graphene oxide layer formed on the NiOx layer; . ≪ / RTI >

In the organic electronic device of the present invention, the hole transport layer may be formed in a single layer structure consisting of a NiOx layer or a graphene oxide layer.

In the above-described organic electronic device of the present invention, the NiOx layer may be formed by a solution process.

In the organic electronic device of the present invention, the lower electrode may be made of a transparent conducting oxide (TCO) electrode, and particularly preferably made of an indium tin oxide (ITO) electrode.

In the organic electronic device of the present invention, the thickness of the graphene oxide layer may be formed in the range of 0.1 to 20nm.

In the organic electronic device of the present invention, the thickness of the NiOx layer may be formed in the range of 0.1 to 100nm.

In the organic electronic device of the present invention, the photoactive layer may include an electron donor material and an electron acceptor material.

In the organic electronic device of the present invention, the substrate is preferably made of a flexible substrate.

In the organic electronic device of the present invention, at least one of the lower electrode and the upper electrode may be formed of an inverted electrode structure.

In the organic electronic device of the present invention, it is preferable that the upper electrode is made of a metal electrode having a work function of 4 to 6 eV.

In the organic electronic device of the present invention, the upper electrode may include at least one of a structure in which LiF and Al are sequentially formed, a structure in which Ca and Al are sequentially formed, a structure in which Ca and Ag are sequentially formed, and a structure in which Mg and Al are sequentially formed. It may be made of a structure.

In the organic electronic device of the present invention, the upper electrode may include at least one of Al, Ag, Au, and Cu.

The organic electronic device manufacturing method of the present invention for solving the above problems, the lower electrode forming step of forming a lower electrode on the substrate; A hole transport layer forming step of forming a hole transport layer on the lower electrode through a solution process; A photoactive layer forming step of forming a photoactive layer on the hole transport layer; And an upper electrode forming step of forming an upper electrode on the photoactive layer through vacuum deposition.

In the method of manufacturing an organic electronic device of the present invention, the hole transport layer forming step includes: forming a graphene oxide layer by spin coating a graphene oxide on the lower electrode; And forming a NiOx layer by spin coating NiOx on the graphene oxide layer.

In the method of manufacturing an organic electronic device of the present invention, the hole transport layer forming step includes: forming a NiOx layer by spin coating NiOx on the lower electrode; Spin-coating graphene oxide on the NiOx layer to form a graphene oxide layer; . ≪ / RTI >

In the method of manufacturing an organic electronic device of the present invention, the hole transport layer forming step may include a step of spin coating NiOx or graphene oxide on the lower electrode.

In the above-described method of manufacturing an organic electronic device, the lower electrode may be made of a transparent conducting oxide (TCO) electrode, and particularly preferably made of an indium tin oxide (ITO) electrode.

In the organic electronic device manufacturing method of the present invention described above, the substrate is preferably a flexible substrate.

The organic electronic device manufacturing method of the present invention described above comprises: forming a passivation layer for protecting a device on the upper electrode after the forming of the upper electrode; It may be made to include more.

According to the present invention, the hole transport layer is formed using a solution process that is easy to process, thereby improving the manufacturing process efficiency of the organic electronic device and reducing the manufacturing cost according to the process efficiency. In addition, according to the present invention, the graphene oxide layer and the NiOx layer can be formed as a double layer as the hole transport layer, thereby effectively reducing the energy barrier between the electrode and the photoactive layer, and improving the characteristics of the hole transport layer. As a result, there is an effect that can provide an organic electronic device with improved energy conversion efficiency.

In addition, according to the present invention, the hole transport layer may be formed on the flexible substrate by a solution process, and thus the thin film organic electronic device may be manufactured.

In addition, the organic electronic device according to the present invention can be applied to various fields such as an OLED display, an OLED display for a flexible flat panel, an organic photovoltaic, an organic thin film transistor (OTFT), and printed electronic materials (Printed Electronics Materials). There are additional possible advantages as well.

1 is a cross-sectional view schematically showing the structure of an organic electronic device according to the present invention.
2 is a flowchart illustrating a method of manufacturing an organic electronic device according to the present invention.
3 is a graph showing a current-voltage curve under AM1.5 solar conditions of the organic electronic device according to Examples 1 to 4 and the organic electronic device according to Comparative Example 1 including no hole transport layer.
4 is a graph showing a current-voltage curve under AM1.5 solar conditions of the organic electronic device according to Examples 5 to 8 of the present invention.
5 is an organic electronic device according to Comparative Example 1 that does not include a hole transport layer, an organic electronic device according to Example 6 using a graphene oxide layer as a hole transport layer, and Example 9 using a graphene oxide layer and a NiOx layer as a double layer A graph showing a current-voltage curve under AM1.5 solar conditions of an organic electronic device according to the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, it is to be understood that the contents described herein are only exemplary embodiments of the present invention, and that various equivalents and modifications may be substituted for them at the time of the present application. DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description, well-known functions or constructions are not described in detail to avoid obscuring the subject matter of the present invention. The following terms are terms defined in consideration of functions in the present invention, and the meaning of each term should be interpreted based on the contents throughout the present specification. The same reference numerals are used for parts having similar functions and functions throughout the drawings.

1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention.

Referring to FIG. 1, the organic electronic device of the present invention has a structure in which a lower electrode 200, a hole transport layer 300, a photoactive layer 400, and an upper electrode 500 are sequentially stacked on a substrate 100. The passivation layer 600 may be further formed on the upper electrode 500.

The substrate 100 is a part that supports each component of the organic electronic device, and the material is not limited, but it is preferable that the substrate 100 is made of a flexible substrate having a certain flexibility in order to provide a thin film organic electronic device. .

The lower electrode 200 is formed on the substrate 100. In this case, the lower electrode 200 is made of a transparent conducting oxide (TCO) electrode, more preferably made of an indium tin oxide (ITO) electrode.

The upper electrode 500 is formed on the photoactive layer 400 to be described later. The upper electrode 500 of the present invention is preferably made of a metal electrode having a work function of 4 to 6eV. More preferably, the upper electrode 500 of the present invention has at least one bilayer of a structure in which LiF and Al are sequentially formed, a structure in which Ca and Al are sequentially formed, a structure in which Ca and Ag are sequentially formed, and a structure in which Mg and Al are sequentially formed. 510 and 530, and most preferably, a structure in which LiF and Al are sequentially formed. However, this is only one example and in addition, the upper part of the present invention may be a single layer structure composed of a metal of any one of aluminum (Al), silver (Ag), gold (Au), and copper (Cu) or a mixture containing two or more thereof. It will be said that the electrode 500 can be formed.

Meanwhile, at least one of the lower electrode 200 and the upper electrode 500 may be formed of an inverted electrode structure. For example, only one of the lower electrode 200 and the upper electrode 500 may have an inverted electrode structure, or both the lower electrode 200 and the upper electrode 500 may have an inverted electrode structure.

The hole transport layer 300 is formed on the lower electrode 200. In particular, the hole transport layer 300 of the present invention is formed including at least one of graphene oxide and NiOx. In addition, the structure may be formed of a double layer (310, 330) structure, as shown in Figure 1, it may be made of a single layer structure. The hole transport layer 300 of the present invention can be formed using a solution process.

When the hole transport layer 300 of the present invention has a double layer structure, a double layer structure in which a graphene oxide layer and a NiOx layer are sequentially formed on the lower electrode 200, or a NiOx layer and graphene oxide layer on the lower electrode 200. The sequentially formed double layer structure may be formed, and the graphene oxide layer and the NiOx layer may be sequentially formed on the lower electrode 200. When the hole transport layer 300 of the present invention is formed in a double layer structure consisting of a graphene oxide layer and a NiOx layer, the energy barrier between the upper electrode 500 and the photoactive layer 400 can be effectively reduced, and the hole transport layer It is possible to improve the characteristics of the 300, as a result there is an effect that can provide an organic electronic device with improved energy conversion efficiency.

On the other hand, the thickness of the graphene oxide layer in the hole transport layer 300 described above is preferably formed in the range of 0.1 to 20nm. If the thickness of the graphene oxide layer is less than 0.1 nm, the property is deteriorated because the uniformity of the layer is reduced. If the thickness of the graphene oxide layer is more than 20 nm, the permeability is rapidly increased as the layer thickness is increased, thereby degrading device characteristics. Because it becomes.

In addition, the thickness of the NiOx layer in the hole transport layer 300 described above is preferably formed in the range of 0.1 to 100nm. If the thickness of the NiOx layer is less than 0.1 nm, the property is deteriorated because the uniformity of the layer is reduced. If the thickness of the NiOx layer is greater than 100 nm, the resistance value increases as the overall thickness of the hole transport layer increases, thereby improving energy conversion efficiency. Because it decreases.

When the hole transport layer 300 of the present invention has a single layer structure, it may be made of only a graphene oxide layer or a NiOx layer. When the hole transport layer 300 is made of only the graphene oxide layer, the thickness thereof is preferably formed in the range of 0.1 to 100 nm, and when the hole transport layer 300 is made of only the NiOx layer, the thickness thereof is in the range of 0.1 to 100 nm. It is preferable to be formed as described above. The photoactive layer 400 is formed on the hole transport layer 300. The photoactive layer 400 of the present invention preferably has a heterojunction structure formed by mixing an electron donor material and an electron acceptor material, or a structure including an organic light emitting material. As the electron donor, polythiofan derivatives, poly (para-phenylene) derivatives, polyflorene derivatives, polyacetylene derivatives, polypyrrole derivatives, polyvinylcarbazole derivatives, polyaniline derivatives and polyphenylenevinylene derivatives can be used. Electronic acceptors include organic compounds such as fullerene (C60 fullerene and C70 fullerene) derivatives and 3,4,9,10-perylenetetracarboxylic bisbenzimidazole (3,4,9,10-perylenetetracarboxylic bisbenzimidazole, PTCBI). Electron-friendly materials, derivatives thereof, and the like can be used, and more preferably, a P3HT: PCBM-71 mixture can be used. On the other hand, the organic light emitting material described above is not limited thereto, and known materials emitting light of blue, red, and green colors may be used.

In addition, a passivation layer 400 may be further formed on the upper electrode 500 as shown in FIG. 1 to stably protect the characteristics of the device from active components such as external impact, moisture, and oxygen. When only the upper electrode 500, which is a metal electrode, is formed, an additional passivation layer 400 may be further formed because penetration of moisture and oxygen by pinholes and cracks is possible. Accordingly, it is possible to stably protect organic electronic devices susceptible to moisture and oxygen.

The organic electronic device of the present invention described above has an effect of improving the manufacturing process efficiency and reducing the manufacturing cost by improving the process efficiency by forming the hole transport layer using an easy process process. In addition, since the graphene oxide layer and the NiOx layer can be formed as a double layer as the hole transport layer, the energy barrier between the electrode and the photoactive layer can be effectively reduced, and the characteristics of the hole transport layer can be improved. There is an effect that can provide an organic electronic device with improved energy conversion efficiency.

In addition, according to the present invention, the hole transport layer may be formed on the flexible substrate by a solution process, thereby additionally producing a thin film organic electronic device. The organic electronic device of the present invention has an advantage that can be applied to various fields such as OLED display, OLED display for flexible flat panel, organic photovoltaic, organic thin film transistor (OTFT) and printed electronic materials (Printed Electronics Materials). Additionally.

2 is a flowchart illustrating a method of manufacturing an organic electronic device according to the present invention.

1 and 2, in the method of manufacturing an organic electronic device of the present invention, a lower electrode is formed on a substrate (S1), a hole transport layer is formed on the lower electrode through a solution process (S3), and a hole transport is performed. Forming a photoactive layer on the layer (S5), and forming an upper electrode on the photoactive layer through vacuum deposition (S7), and after forming the upper electrode, a passivation layer for device protection on the upper electrode It can be made, including forming more.

Forming the lower electrode on the substrate (S1) can be made as follows.

An electrode pattern is formed by depositing a material forming the lower electrode on the substrate. In this case, a transparent conducting oxide (TCO) may be used as the lower electrode forming material, and indium tin oxide (ITO) is preferably used in the description of FIG. 1. On the other hand, there is no limitation to the substrate used in the step S1, it is preferable that the flexible substrate is used to thin the organic electronic device as described above in FIG.

Thereafter, a hole transport layer is formed on the lower electrode (S3).

The hole transport layer is formed through a solution process, it may be made of a single layer or a double layer structure.

When the hole transport layer has a double layer structure, the graphene oxide layer may be formed by spin coating, and then the NiOx layer may be sequentially formed by spin coating a NiOx solution made by a sol-gel method. Alternatively, the NiOx solution made by the sol-gel method may be spin coated to form a NiOx layer, and then the graphene oxide layer may be formed through spin coating. On the other hand, when the hole transport layer is formed in a single layer structure, the hole transport layer of the present invention may be formed in a single layer structure in which only a NiOx layer or a graphene oxide layer is formed by the above-described method. Other explanations are the same as those described above with reference to FIG. According to this, it is possible to form the hole transport layer by a simple solution process, it is possible to improve the manufacturing process efficiency compared to the conventional, it is possible to reduce the manufacturing cost.

Thereafter, a photoactive layer is formed on the hole transport layer (S5). The method of forming the photoactive layer may be performed by, for example, preparing a photoactive layer solution in which the photoactive layer material is dissolved, and spin coating the prepared photoactive layer solution on the hole transport layer. In this case, a mixture of an electron donor material and an electron acceptor material may be used as the photoactive layer material. As the electron donor, polythiofan derivatives, poly (para-phenylene) derivatives, polyflorene derivatives, polyacetylene derivatives, polypyrrole derivatives, polyvinylcarbazole derivatives, polyaniline derivatives and polyphenylenevinylene derivatives can be used. Electronic acceptors include organic compounds such as fullerene (C60 fullerene and C70 fullerene) derivatives and 3,4,9,10-perylenetetracarboxylic bisbenzimidazole (3,4,9,10-perylenetetracarboxylic bisbenzimidazole, PTCBI). Electron-friendly materials, derivatives thereof, and the like can be used, and more preferably, P3HT: PCBM-71 mixture can be used. Meanwhile, the photoactive layer material may include an organic light emitting material, and more specifically, a known material emitting light of blue, red, and green may be used, as described above with reference to FIG. 1.

Thereafter, an upper electrode is formed on the photoactive layer by vacuum deposition (S7). The upper electrode may be formed of a metal electrode, and more specifically, a structure in which LiF and Al are sequentially deposited on the photoactive layer, a structure in which Ca and Al are sequentially deposited, a structure in which Ca and Ag are sequentially deposited, and Mg and Al are sequentially At least one of the deposited structures may be formed, and most preferably, may be formed of a structure in which LiF and Al are sequentially deposited on the photoactive layer. In addition, the description of the upper electrode is omitted as described above in the description of FIG. 1.

On the other hand, after forming the upper electrode, it is preferable to form a passivation layer on the upper electrode to stably protect the organic electronic device vulnerable to moisture and oxygen.

Hereinafter, the organic electronic device manufactured according to each embodiment of the present invention is compared with the conventional organic electronic device. More specifically, Examples 1 to 4 are organic electronic devices in which a hole transport layer is formed of a single NiOx layer, and Examples 5 to 8 are organic electronic devices in which a hole transport layer is formed of a graphene oxide layer single layer. In addition, Examples 9 to 10 are organic electronic devices in which the hole transport layer is formed in a double layer structure consisting of a graphene oxide layer and a NiOx layer. On the other hand, Comparative Example 1 is an organic electronic device in which no hole transport layer is formed, and Comparative Example 2 is an organic electronic device in which a PEDOT: PSS layer is formed as the hole transport layer.

1. Examples 1-4

After forming an indium thin oxide (ITO) electrode pattern as a lower electrode on the substrate, the acetone, methanol, and isopropyl alcohol were washed with an ultrasonic cleaner for 10 minutes in order, followed by UV / Ozone treatment for 10 minutes. After the spin-coated NiOx solution made by the sol-gel method on the cleaned ITO electrode to form a hole transport layer as a single layer consisting of a NiOx layer. At this time, the thickness of the NiOx layer was changed by changing the spin rate. More specifically, when spin-coating at 1000 rpm, Example 1, when spin-coating at 2000 rpm, Example 2, when spin-coating at 3000 rpm, Example 3, spin-coating at 4000 rpm Is referred to as Example 4. Since the above Examples 1 to 4 were all heated for 30 minutes on a hotplate maintained at 280 ℃ in air to form a NiOx layer. After the NiOx layer was formed, P3HT (poly (3-hexylthiophene)) and PCBM-71 were dissolved in a dichlorobenzene solvent at 1.5% by weight as a photoactive layer material, and then a photoactive layer solution was prepared and then prepared on the NiOx layer. The photoactive layer solution was spin-coated at 700 rpm and heat-treated at 130 ° C. for 30 minutes to form a 100 nm thick photoactive layer. After the photoactive layer was formed, the upper electrode, a LiF / Al metal electrode, was formed by using a thermal deposition and a shadow mask. In more detail, LiF was deposited at a thickness of 0.5 nm at a rate of 0.1 ms / sec, and Al electrode was deposited at a thickness of 100 nm at a rate of 2 ms / sec. After forming the upper electrode, the passivation of the organic electronic device of the present invention was performed by photocuring using a passivation glass, a moisture absorbent and a photocurable resin.

2. Examples 5-8

After forming an indium thin oxide (ITO) electrode pattern as a lower electrode on the substrate, acetone, methanol, and isopropyl alcohol were washed with an ultrasonic cleaner for 10 minutes in order, followed by UV / Ozone treatment for 10 minutes. A graphene oxide layer was then formed on the cleaned ITO electrode as a hole transport layer by spin coating. In order to obtain an optimized thickness of the graphene oxide layer, the number of spin coatings was changed to form a layer. More specifically, the case of spin coating once in Example 5 and the case of spin coating twice in Example 6 and the case of spin coating three times in Example 7, the case of spin coating five times is called Example 8. After the spin coating, the above Examples 5 to 8 were all heated for 20 minutes on a hotplate maintained at 200 ° C. in a glove box to form a graphene oxide layer. After dissolving P3HT (poly (3-hexylthiophene)) and PCBM-71 in dichlorobenzene solvent at 1.5% by weight as a photoactive layer material, a photoactive layer solution was prepared by filtering and spin-coated at 700 rpm on the graphene oxide layer. Thereafter, heat treatment was performed at 130 ° C. for 30 minutes to form a photoactive layer having a thickness of 100 nm. After the photoactive layer was formed, the upper electrode, a LiF / Al metal electrode, was formed by using a thermal deposition and a shadow mask. At this time, the LiF layer was deposited at a thickness of 0.5 nm at a rate of 0.1 μs / sec, and the Al electrode was deposited at a thickness of 100 nm at a rate of 2-3 μs / sec. After forming the upper electrode, the passivation of the organic electronic device of the present invention was performed by photocuring using a passivation glass, a moisture absorbent and a photocurable resin.

3. Example 9

After forming an indium thin oxide (ITO) electrode pattern as a lower electrode on the substrate, acetone, methanol, and isopropyl alcohol were washed with an ultrasonic cleaner for 10 minutes in order, followed by UV / Ozone treatment for 10 minutes. A double layer structured hole transport layer was formed by forming a graphene oxime layer on the ITO electrode by the method described above and then forming a NiOx layer. After dissolving P3HT (poly (3-hexylthiophene)) and PCBM-71 in a dichlorobenzene solvent at 1.5% by weight as a photoactive layer material to prepare a photoactive layer solution by filtering, spin coating at 700 rpm on a NiOx layer, Heat treatment was performed at 130 ° C. for 30 minutes to form a photoactive layer having a thickness of 100 nm. After the photoactive layer was formed, the upper electrode, a LiF / Al metal electrode, was formed by using a thermal deposition and a shadow mask. At this time, LiF was deposited at a thickness of 0.5 nm at a rate of 0.1 mW / sec, and Al electrode was deposited at a thickness of 100 nm at a rate of 2-3 mW / sec. After forming the metal electrode, the passivation of the organic electronic device of the present invention was performed by photocuring using a passivation glass, a moisture absorbent and a photocurable resin.

4. Example 10

After forming an indium thin oxide (ITO) electrode pattern as a lower electrode on the substrate, acetone, methanol, and isopropyl alcohol were washed with an ultrasonic cleaner for 10 minutes in order, followed by UV / Ozone treatment for 10 minutes. After the NiOx layer was formed on the ITO electrode by the method described above, a graphene oxide layer was formed to form a hole transport layer having a double layer structure. After dissolving P3HT (poly (3-hexylthiophene)) and PCBM-71 in dichlorobenzene solvent at 1.5% by weight as a photoactive layer material, a photoactive layer solution was prepared by filtering and spin coating at 700 rpm on the graphene oxide layer. Then, heat treatment was performed at 130 ° C. for 30 minutes to form a photoactive layer having a thickness of 100 nm. After the photoactive layer was formed, the upper electrode, a LiF / Al metal electrode, was formed by using a thermal deposition and a shadow mask. LiF was deposited at a thickness of 0.5 nm at a rate of 0.1 ms / sec, and Al electrode was deposited at a thickness of 100 nm at a rate of 2-3 mA / sec. After forming the metal electrode, the passivation of the organic electronic device of the present invention was performed by photocuring using a passivation glass, a moisture absorbent and a photocurable resin.

5. Comparative Example 1

After forming an indium thin oxide (ITO) electrode pattern as a lower electrode on the substrate, acetone, methanol, and isopropyl alcohol were washed with an ultrasonic cleaner for 10 minutes in order, followed by UV / Ozone treatment for 10 minutes. Thereafter, without forming both the NiOx layer and the graphene oxide layer described above on the ITO electrode, P3HT (poly (3-hexylthiophene)) and PCBM-71 as a photoactive layer material directly on the ITO electrode in 1.5 weight of dichlorobenzene solvent After dissolving and filtering at%, a photoactive layer solution was prepared, spin-coated at 700 rpm, and heat-treated at 130 ° C. for 30 minutes to form a photoactive layer having a thickness of 100 nm. After the photoactive layer was formed, the upper electrode, a LiF / Al metal electrode, was formed by using a thermal deposition and a shadow mask. LiF was deposited at a thickness of 0.5 nm at a rate of 0.1 ms / sec, and Al electrode was deposited at a thickness of 100 nm at a rate of 2-3 mA / sec. After the metal electrode was formed, the device was passivated by photocuring using a passivation glass, a moisture absorbent, and a photocurable resin.

6. Comparative Example 2

After forming an indium thin oxide (ITO) electrode pattern as a lower electrode on the substrate, acetone, methanol, and isopropyl alcohol were washed with an ultrasonic cleaner for 10 minutes in order, followed by UV / Ozone treatment for 10 minutes. After forming a PEDOT: PSS layer as a hole transporting layer on the ITO electrode by spin coating, P3HT (poly (3-hexylthiophene)) and PCBM-71 were dissolved in a dichlorobenzene solvent at 1.5% by weight in a photoactive layer material and filtered. After preparing a photoactive layer solution, spin-coated at 700 rpm, and heat-treated at 130 ℃ 30 minutes to form a 100nm thick photoactive layer. After the photoactive layer was formed, the upper electrode, a LiF / Al metal electrode, was formed by using a thermal deposition and a shadow mask. LiF was deposited at a thickness of 0.5 nm at a rate of 0.1 mA / sec, and Al electrode was deposited at a thickness of 100 nm at a rate of 2-3 mA / sec. After the metal electrode was formed, the device was passivated by photocuring using a passivation glass, a moisture absorbent, and a photocurable resin.

Table 1 briefly shows the hole transport layer structure of the organic electronic device described in Examples 1 to 10 and Comparative Examples 1 and 2.

Table 2 shows the characteristics evaluation results of the organic electronic devices according to Examples 1 to 10 and Comparative Examples 1 to 2 according to the present invention. (PCE) was measured and shown. The characteristics of the organic electronic device was measured by measuring the voltage (V) and current (I) at 25 ℃ using an artificial solar irradiation device (AM1.5 Solar simulator, Asahi spectra Inc., MAX-302HAL) of 100 ㎽ / ㎠ Short circuit current, open voltage, curve factor and energy conversion efficiency were measured.

[Table 1]

[Table 2]

In Examples 1 to 4 using the NiOx layer as a single layer, it can be seen that the energy conversion efficiency is superior to Comparative Example 1 in which the hole transport layer is not used. In addition, in Examples 1 to 4, Example 4 in which the NiOx layer was formed under the conditions of 4000 rpm showed the best characteristics, and in Example 1 in which the NiOx layer was formed under the 1000 rpm conditions, the resistance increased as the hole transport layer became thicker. Therefore, it can be seen that the energy conversion efficiency (PCE) decreases because the curve factor (FF) decreases.

In the case of Examples 5 to 8 using the graphene oxide layer as a single layer, it can be seen that the energy conversion efficiency also has all excellent properties compared to Comparative Example 1 without using the hole transport layer. In addition, it can be seen that the organic electronic device of Example 7, which was formed by coating three times, exhibits the best characteristics. On the other hand, the organic electronic devices of Examples 5 and 6 coated with 1 to 2 times had a decreased property because the uniformity of the graphene oxide thin film decreased, and the organic electronic devices of Example 8 coated with 5 times had a sharply high permeability. It can be seen that as the short-circuit current (Jsc) is reduced, the organic electronic device characteristics are reduced.

In particular, in the organic electronic device according to Example 9 using the graphene oxide layer and the NiOx layer as a double layer, Jsc, Voc, FF, and PCE were 8.71 mA / cm ² , 0.60 V, 66.44%, and 3.48, respectively. % Is indicated. This result, it can be seen that in Comparative Example 2 exhibits superior characteristics than the organic electronic device using PEDOT: PSS as the hole transport layer.

3 to 5 are graphs showing current-voltage curves under AM1.5 solar conditions of organic electronic devices according to examples and comparative examples of the present invention.

3 is a graph showing a current-voltage curve under AM1.5 solar conditions of the organic electronic device according to Examples 1 to 4 and the organic electronic device according to Comparative Example 1 including no hole transport layer. As described above, in Examples 1 to 4, it can be seen that Jsc and Voc characteristics are all superior to Comparative Example 1 in which the hole transport layer is not used.

4 is a graph illustrating a current-voltage curve under AM1.5 solar conditions of an organic electronic device according to Examples 5 to 8, wherein Jsc and Voc characteristics are mostly compared with those of Comparative Example 1 shown in FIG. It can be seen that excellent.

5 is an organic electronic device according to Comparative Example 1 that does not include a hole transport layer, an organic electronic device according to Example 7 using a graphene oxide layer as a hole transport layer, and Example 9 using a graphene oxide layer and a NiOx layer as a double layer A graph showing a current-voltage curve under AM1.5 solar conditions of an organic electronic device according to the present invention, in which Examples 7 and 9 have superior characteristics to Comparative Example 1, in particular, Example 9 in which the hole transport layer is formed of a double layer. In the case of it can be seen that it has the most excellent properties.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, Those skilled in the art will appreciate that many suitable modifications and variations are possible in light of the present invention. Accordingly, all such suitable modifications and variations and equivalents should be considered to be within the scope of the present invention.

100: substrate
200: lower electrode
300: hole transport layer
400: photoactive layer
500: upper electrode
600: passivation layer

Claims (23)

Board;
A lower electrode formed on the substrate;
A hole transport layer formed on the lower electrode and including at least one of graphene oxide and NiOx;
A photoactive layer formed on the hole transport layer;
An upper electrode formed on the photoactive layer;
Organic electronic device comprising a.
The method according to claim 1,
The hole transport layer,
A graphene oxide layer formed on the lower electrode;
A NiO x layer formed on the graphene oxide layer;
Organic electronic device comprising a.
The method according to claim 1,
The hole transport layer,
A NiOx layer formed on the lower electrode;
A graphene oxide layer formed on the NiOx layer;
Organic electronic device comprising a.
The method according to claim 1,
The hole transport layer,
An organic electronic device comprising a NiOx layer or a graphene oxide layer.
The method according to any one of claims 2 to 4,
The NiOx layer,
An organic electronic device formed by a solution process.
5. The method according to any one of claims 1 to 4,
The lower electrode,
An organic electronic device, characterized in that it is a transparent conducting oxide (TCO) electrode.
The method of claim 6,
The lower electrode,
An organic electronic device comprising an indium tin oxide (ITO) electrode.
The method according to any one of claims 2 to 4,
The thickness of the graphene oxide layer, the organic electronic device, characterized in that 0.1 to 20nm.
The method according to any one of claims 2 to 4,
The thickness of said NiOx layer is 0.1-100 nm, The organic electronic device.
5. The method according to any one of claims 1 to 4,
The photoactive layer,
An organic electronic device comprising an electron donor material and an electron acceptor material.
5. The method according to any one of claims 1 to 4,
The substrate,
An organic electronic device, characterized in that it is a flexible substrate.
5. The method according to any one of claims 1 to 4,
At least one of the lower electrode and the upper electrode has an inverted electrode structure.
5. The method according to any one of claims 1 to 4,
The upper electrode,
An organic electronic device comprising a metal electrode having a work function of 4 to 6 eV.
The method according to claim 13,
The upper electrode,
An organic electronic device comprising at least one of a structure in which LiF and Al are sequentially formed, a structure in which Ca and Al are sequentially formed, a structure in which Ca and Ag are sequentially formed, and a structure in which Mg and Al are sequentially formed.
The method according to claim 13,
The upper electrode,
An organic electronic device comprising at least one of Al, Ag, Au, and Cu.
5. The method according to any one of claims 1 to 4,
An organic electronic device further comprising a passivation layer formed on the upper electrode.
Forming a lower electrode on the substrate;
Forming a hole transport layer including at least one of graphene oxide and NiOx on the lower electrode through a solution process;
A photoactive layer forming step of forming a photoactive layer on the hole transport layer;
An upper electrode forming step of forming an upper electrode on the photoactive layer through vacuum deposition; Organic electronic device manufacturing method comprising a.
18. The method of claim 17,
The hole transport layer forming step,
Forming a graphene oxide layer by spin-coating graphene oxide on the lower electrode;
Forming a NiOx layer by spin coating NiOx on the graphene oxide layer;
Organic electronic device manufacturing method comprising a.
18. The method of claim 17,
The hole transport layer forming step,
Spin-coating NiOx on the lower electrode to form a NiOx layer;
Spin-coating graphene oxide on the NiOx layer to form a graphene oxide layer;
Organic electronic device manufacturing method comprising a.
18. The method of claim 17,
The hole transport layer forming step,
Spin coating NiOx or graphene oxide on the lower electrode;
Organic electronic device manufacturing method comprising a.
The method according to any one of claims 17 to 20,
The lower electrode,
The organic thin film solar cell manufacturing method characterized in that the TCO (Transparent conducting oxide) electrode.
The method according to any one of claims 17 to 20,
After the upper electrode forming step,
Forming a passivation layer for protecting the device on the upper electrode; Organic electronic device manufacturing method further comprising.
The method according to any one of claims 17 to 20,
The substrate,
A method of manufacturing an organic electronic device, which is a flexible substrate.

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