KR101734369B1 - Organic electronic device - Google Patents

Abstract

The present disclosure provides organic electronic devices.

Description

[0001] ORGANIC ELECTRONIC DEVICE [0002]

This specification claims the benefit of Korean Patent Application No. 10-2013-0116111, filed on September 30, 2013, to the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

The present invention relates to an organic electronic device including a transparent electrode as a lower electrode.

With the emergence of the new and renewable energy industry together with the high-tech information technology industry, there is a growing interest in transparent electrodes having both electric conductivity and light transmittance. Transparent electrodes in organic electronic devices must transmit light through a thin transparent substrate, and at the same time have good electrical conductivity.

Transparent Conducting Oxide (TCO), which is manufactured in the form of a thin film, is a typical transparent electrode material. The transparent conductive oxide generally refers to an oxide-based degenerate semiconductor electrode having a high optical transparency (not less than 85%) and a relatively low specific resistance (1 10 ^-3 ? Cm) in the visible light region, Are used as core electrode materials for functional thin films such as antistatic films and electromagnetic wave shielding, flat panel displays, solar cells, touch panels, transparent transistors, flexible optoelectronic devices, and transparent optoelectronic devices.

However, the transparent electrode made of transparent conductive oxide has lower electric conductivity than metal (specific resistance ~ 10 ^-8 ? Cm) used for electrodes such as silver and aluminum, so that as the light emitting area becomes wider, There is a performance degradation problem caused by the increase in the number of bits. In addition, indium tin oxide (ITO), which is the most commonly used TCO, causes price competitiveness to deteriorate due to continuous price increase due to depletion of In. Furthermore, when applied to the upper electrode, the lower organic layer is damaged due to the characteristics of the process, and brittleness is brittleness. This is a major cause of degradation of lifetime and driving voltage of the device when it is used as an electrode of a flexible device due to a rise in raw material costs. Therefore, it is necessary to develop electrodes having high visible light transmittance, low resistivity and brittleness by using a cheap metal rather than a rare metal, while being compatible with existing processes.

C. W. Tang, S. A. Vanslyke and C. H. Chen, J. Appl. Phys 1989, 65, 3610

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic electronic device including a transparent electrode as a lower electrode.

One embodiment of the present disclosure includes a lower electrode; An upper electrode facing the lower electrode; And an organic layer disposed between the lower electrode and the upper electrode,

Wherein the lower electrode comprises a first organic compound layer comprising a compound represented by Formula 1 below; And a transparent electrode comprising at least one conductive unit including a metal layer provided in contact with the first organic material layer.

[Chemical Formula 1]

Each of R1 to R6 is hydrogen; A halogen group; Nitrile group (-CN); A nitro group (-NO ₂ ); A sulfonyl group (-SO ₂ R); Sulfoxide group (-SOR); A sulfonamide group (-SO ₂ NR _2); Sulfonate groups (-SO ₃ R); A trifluoromethyl group (-CF _3); Ester group (-COOR); An amide group (-CONHR or -CONRR '); A substituted or unsubstituted straight or branched chain C1 to C12 alkoxy group; A substituted or unsubstituted straight or branched chain C1 to C12 alkyl group; A substituted or unsubstituted straight or branched chain C2 to C12 alkenyl group; A substituted or unsubstituted aromatic or non-aromatic heterocyclic group; A substituted or unsubstituted aryl group; A substituted or unsubstituted mono- or di-arylamine group; And a substituted or unsubstituted aralkylamine group,

R and R 'are each a substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted 5- to 7-membered aliphatic cyclic group.

The transparent electrode in this specification has a high electrical conductivity.

Further, the transparent electrode in this specification has high light transmittance.

Further, the transparent electrode of the present specification can be made larger.

In addition, when the transparent electrode of the present invention is included in an organic electronic device, the lifetime of the organic electronic device can be improved and the stability of the device can be improved.

In addition, when the transparent electrode of the present invention is included in an organic electronic device, the efficiency of the organic electronic device can be improved.

1 to 6 show the structure of a transparent electrode according to one embodiment of the present invention.
7 and 8 are TEM images when a metal layer is formed on the first organic material layer in this specification.
Figs. 9 to 12 are SEM (Scanning Electron Microscope) images of the aggregation phenomenon in the case of forming the metal layer.
13 and 14 illustrate a normal structure organic light emitting device according to an embodiment of the present invention.
15 shows JV characteristic data of the organic light emitting devices of Examples 7 to 9 and Comparative Example 15 of this specification.
16 shows lifetime-related data of the organic light-emitting devices of Examples 7 to 9 and Comparative Example 15 of this specification.

Hereinafter, the present invention will be described in more detail.

One embodiment of the present disclosure includes a lower electrode; An upper electrode facing the lower electrode; And an organic layer disposed between the lower electrode and the upper electrode,

Wherein the lower electrode comprises a first organic material layer including a compound represented by Formula 1; And a transparent electrode comprising at least one conductive unit including a metal layer provided in contact with the first organic material layer.

Also, according to one embodiment of the present invention, the R1 to R6 in the formula (1) may all be a nitrile group (-CN).

Also, according to one embodiment of the present invention, the compound represented by Formula 1 may be any one of Formula 1-1 to 1-6.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

According to an embodiment of the present invention, the transparent electrode may have one conductive unit.

Figure 1 illustrates a transparent electrode according to one embodiment of the present disclosure. More specifically, FIG. 1 shows a transparent electrode having one conductive unit, and the metal layer 201 is provided on the first organic layer 101.

According to an embodiment of the present invention, the transparent electrode may include two or more conductive units sequentially stacked.

Figure 4 illustrates a transparent electrode according to one embodiment of the present disclosure. Specifically, FIG. 2 shows a transparent electrode having two conductive units, in which a metal layer 202 is provided on a first organic layer 102 on a conductive unit having a metal layer 201 on the first organic layer 101 And the other conductive units are stacked.

According to an embodiment of the present invention, the transparent electrode may be provided on a substrate. Specifically, according to one embodiment of the present invention, the transparent electrode is provided on the substrate, and the conductive unit in contact with the substrate may include the first organic layer on the substrate.

According to an embodiment of the present invention, the metal layer may include one or more selected from the group consisting of a metal having a work function of 2 eV or more and 6 eV or less and a metal alloy of two or more thereof.

According to an embodiment of the present invention, the metal having a work function of 2 eV to 6 eV may be Au, Ag, Al, Ca, Mg, Yb, Sm, Cs, Ba, Li, Rb, Cu, have.

Specifically, according to an embodiment of the present invention, the metal layer may be made of Ag.

According to an embodiment of the present invention, the metal layer is capable of lowering surface energy by interaction with the first organic layer. Specifically, the surface energy of the metal layer with respect to the first organic material layer is reduced, so that aggregation on the first organic material layer can be suppressed. Therefore, according to one embodiment of the present invention, when the metal layer is formed of a thin metal layer, a stable transparent electrode can be formed. Specifically, according to an embodiment of the present invention, the first organic layer may be a seed layer of the metal layer.

In the case of forming a metal layer by depositing a metal, the metal particles may be aggregated to increase the sheet resistance value of the metal layer, thereby lowering the electrical conductivity. Specifically, when a lower electrode is formed by depositing a metal on a substrate such as glass, the electric conductivity is lowered due to the accumulation of metal, and the function as an electrode is deteriorated. In addition, the electrode has a low light transmittance due to the aggregation of the metal. However, in the case of forming a transparent electrode by depositing metal particles on the first organic material layer of the present invention, the first organic material layer functions as a seed layer, thereby lowering the energy of the interface between the two materials, There is no aggregation phenomenon. Specifically, according to one embodiment of the present invention, when Ag is deposited as the material of the metal layer in the first organic material layer made of the compound represented by Formula 1-1, there is no aggregation of Ag particles. Therefore, the transparent electrode of the present invention can have a high electric conductivity and a low sheet resistance, and further, can have high light transmittance because the metal of the metal layer can spread evenly and maintain a seamless morphology.

7 is an SEM image of a first organic layer made of a compound represented by Formula 1-1 and having a thickness of 20 nm, and Ag having a thickness of 5 nm deposited as a metal layer.

FIG. 8 is an SEM image of a first organic layer made of the compound represented by Formula 1-1 and having a thickness of 20 nm, followed by deposition of Ag to a thickness of 10 nm as a metal layer.

9 is an SEM image of an organic layer formed of a compound represented by the following Chemical Formula 2, not a first organic layer, to a thickness of 20 nm, followed by deposition of Ag to a thickness of 5 nm.

10 is an SEM image of an organic material layer formed of a compound represented by the following Chemical Formula 2, which is not the first organic material layer, to a thickness of 20 nm, followed by deposition of Ag to a thickness of 10 nm.

(2)

11 is an SEM image of deposition of Ag on a glass substrate to a thickness of 5 nm.

12 is an SEM image of deposition of Ag on the glass substrate to a thickness of 10 nm.

As shown in FIGS. 7 and 8, when the first organic material layer is doped with a metal, the metal does not aggregate and the metal of the metal layer is evenly distributed.

On the other hand, as shown in FIGS. 9 to 12, when a metal layer is deposited on a glass substrate or an organic material layer other than the first organic material layer, metal clumping occurs. In the case of FIG. 10, there is a middle intermediate depressed portion of the metal layer, and the roughness of the surface is severe, which means that the film formation of the metal layer itself is poor.

According to one embodiment of the present invention, the organic layer or the inorganic layer may be further included on the conductive unit.

According to an embodiment of the present invention, the second organic layer may include a compound represented by Formula 1.

According to one embodiment of the present disclosure, the inorganic layer may comprise ITO; IZO; IZTO; ATO; AZO; GZO; FTO; ZTO; ZnO; FZO; IGZO; WO ₃ ; ZrO _3; V ₂ O ₇ ; MoO ₃ ; Or ReO < ₃ >.

According to an embodiment of the present invention, the transparent electrode may have one conductive unit, and the second organic layer or the inorganic layer may be provided on the metal layer.

Figures 2 and 3 illustrate a transparent electrode according to one embodiment of the present disclosure. 2 illustrates a transparent electrode having a metal layer 201 on a first organic layer 101 and a second organic layer 301 on a metal layer 201. FIG.

3 shows a transparent electrode having a metal layer 201 on one organic layer 101 and an inorganic layer 401 on the metal layer 201. In FIG.

According to an embodiment of the present invention, the transparent electrode may be one in which two conductive units are sequentially stacked, and the second organic layer or the inorganic layer is provided on the metal layer of the conductive unit disposed closest to the upper electrode have.

5 and 6 illustrate a transparent electrode according to an embodiment of the present invention. 5 illustrates another example in which another conductive unit having a metal layer 202 on a first organic layer 102 is laminated on a conductive unit having a metal layer 201 on a first organic layer 101, And the second organic layer 301 is provided on the first transparent electrode 201.

6 shows another example in which another conductive unit having the metal layer 202 on the first organic layer 102 is laminated on the conductive unit having the metal layer 201 on the first organic layer 101, And the inorganic layer 401 is provided on the transparent electrode.

According to an embodiment of the present invention, the thickness of the first organic layer may be 5 nm or more and 50 nm or less. Specifically, the thickness of the first organic material layer may be 20 nm or more and 40 nm or less.

According to an embodiment of the present invention, the thickness of the metal layer may be 1 nm or more and 20 nm or less. Specifically, the thickness of the metal layer may be 2 nm or more and 15 nm or less.

According to an embodiment of the present invention, the thickness of the second organic layer or the inorganic layer may be 10 nm or more and 200 nm or less. Specifically, the thickness of the second organic material layer may be 10 nm or more and 30 nm or less. Further, the thickness of the inorganic material layer may be 10 nm or more and 30 nm or less.

According to an embodiment of the present invention, the organic electronic device may be a normal structure, an inverted structure, or a tandem structure.

According to an embodiment of the present disclosure, in a normal structure, the upper electrode may be a cathode, and the lower electrode may be an anode.

According to an embodiment of the present disclosure, in an inverted structure, the upper electrode may be an anode, and the lower electrode may be a cathode.

According to an embodiment of the present invention, the organic electronic device may be an organic light emitting device.

According to an embodiment of the present invention, the organic electronic device includes a lower electrode; An upper electrode facing the lower electrode; And an organic light emitting device including at least one organic layer disposed between the lower electrode and the upper electrode and including a light emitting layer.

According to an embodiment of the present invention, the organic material layer of the organic light emitting device further includes at least one selected from the group consisting of a light emitting layer, a hole transporting layer, a hole blocking layer, an electron blocking layer, an electron transporting layer, and an electron injecting layer.

According to an embodiment of the present invention, the organic layer of the organic light emitting device includes a light emitting layer.

According to an embodiment of the present invention, the light emitting layer of the organic light emitting device includes a host and a dopant.

According to an embodiment of the present invention, the organic material layer of the organic light emitting device includes a layer that simultaneously transports electrons and emits light.

According to an embodiment of the present invention, the organic layer of the organic light emitting device includes a layer that simultaneously emits light and transports electrons and / or electrons.

When the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

According to an embodiment of the present invention, the organic electronic device may be an organic solar cell.

According to an embodiment of the present invention, the organic electronic device includes a lower electrode; An upper electrode facing the lower electrode; And at least one organic layer disposed between the lower electrode and the upper electrode and including a photoactive layer.

According to an embodiment of the present invention, the organic layer of the organic solar battery includes a photoactive layer.

According to an embodiment of the present invention, the organic layer of the organic solar cell further includes at least one selected from the group consisting of a photoactive layer, an electron donor and an electron acceptor.

According to an embodiment of the present invention, the organic material layer of the organic solar cell may be a layer having the electron donor and / or the electron acceptor simultaneously as the photoactive layer.

According to an embodiment of the present invention, when the organic solar cell receives a photon from an external light source, electrons and holes are generated between the electron source and the electron acceptor. The generated holes are transported to the anode through the electron donor layer.

According to an embodiment of the present invention, the organic layer of the organic solar cell may include two or more kinds of materials.

According to one embodiment of the present disclosure, the organic solar cell further comprises an additional organic layer. The organic solar cell can reduce the number of organic layers by using organic materials having various functions at the same time.

According to one embodiment of the present disclosure, the organic electronic device may be an organic transistor.

According to one embodiment of the present disclosure, there is provided an organic transistor including a source, a drain, a gate, and one or more organic layers.

According to an embodiment of the present invention, the organic electronic device may be an organic transistor including a source, a drain, a gate, and one or more organic layers.

According to an embodiment of the present invention, the organic transistor may further include an insulating layer. The insulating layer may be located on the substrate and the gate.

13 and 14 illustrate a normal structure organic light emitting device according to an embodiment of the present invention.

13 shows an organic light emitting device in which a metal layer 201 is provided on the first organic material layer 101 as an anode, Cahtode means a cathode, HTL means a hole transporting layer, EML means a light emitting layer, Transport layer. However, the present invention is not limited thereto, and each layer except for the electrode may be omitted, or a separate layer may be added.

14 is an organic light emitting device having a transparent electrode having a metal layer 201 on a first organic layer 101 as an anode and a second organic layer 301 on a metal layer 201. Cahtode has a cathode HTL means a hole transporting layer, EML means a light emitting layer, and ETL means an electron transporting layer. However, the present invention is not limited thereto, and each layer except for the electrode may be omitted, or a separate layer may be added.

According to one embodiment of the present disclosure, the transparent electrode has a low sheet resistance value, i.e., a high electrical conductivity.

According to an embodiment of the present invention, the transparent electrode may have a resistance of 2 Ω / □ or more and 100 Ω / □ or less. Specifically, the sheet resistance value of the transparent electrode may be 5 Ω / □ or more and 80 Ω / □ or less.

Due to the low surface resistance value of the transparent electrode in this specification, the organic electronic device can be normally driven without applying an excessive voltage. Therefore, when the transparent electrode is provided, the lifetime of the organic electronic device can be increased. That is, the stability of the organic electronic device can be improved.

In addition, the transparent electrode of the present invention has a low sheet resistance and a high light transmittance.

According to an embodiment of the present invention, the light transmittance of the transparent electrode may be 40% or more and 80% or less.

The sheet resistance value and the light transmittance of the present invention are measured by forming electrodes on sodalime glass having a thickness of 700 탆 and encapsulating the electrodes with sodalime glass having a thickness of 1000 탆, And the light transmittance is measured by measuring the transmittance of light having a wavelength of 550 nm.

When an electrode is formed using only an inorganic layer as an upper electrode by using a deposition process, there is a disadvantage that a defective rate is high. Specifically, when ITO or IZO is formed as an upper electrode by the sputtering method, the upper electrode is damaged due to sputtering, and the ratio of the electrode to the electrode can not be high. On the contrary, the transparent electrode of the present invention can be deposited without damaging even when the first inorganic material layer is deposited by a sputtering method. This is because the metal layer can prevent sputter damage.

In the case of an upper electrode using generally used Mg: Ag or Ca: Ag, it is difficult to form a large-area electrode due to a high sheet resistance value. That is, the upper electrode of Mg: Ag or Ca: Ag is required to ensure the electrical stability of Mg and Ca by Ag, but when used as an upper electrode, the thickness of the entire metal layer is as thin as 20 nm or less, It is difficult to secure the oxidation stability of the metal. This increases the surface resistance of the surface or causes deterioration of the charge injection characteristics. In addition, if there is no surface energy degradation characteristic due to the seed layer, the above characteristics are accelerated due to agglomeration of Ag or the like, and visible light absorption due to surface plasmon resonance (SPR) There is a problem that the effect is increased and the transmittance is decreased. On the other hand, the transparent electrode of the present invention can be realized as a large-area upper electrode by virtue of the low sheet resistance and high light transmittance without causing the metal layer to scoop.

Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.

≪ Example 1 > - Surface resistance and light transmittance

A first organic layer made of the compound represented by Formula 1-1 and a metal layer made of Ag having a thickness of 5 nm are sequentially laminated on a soda lime glass having a thickness of 700 mu m to form a transparent electrode Respectively. The sheet resistance was measured by encapsulating the transparent electrode with sodalime glass having a thickness of 700 탆, and the light transmittance was measured by measuring the transmittance of light having a wavelength of 550 nm.

The sheet resistance of the transparent electrode measured in Example 1 was 75? / ?, and the light transmittance was 55%.

≪ Example 2 > - Surface resistance and light transmittance

A first organic layer made of a compound represented by the above formula (1-1) and a metal layer made of Ag having a thickness of 7 nm are sequentially laminated on a sodalime glass having a thickness of 700 mu m to form a transparent electrode Respectively. The sheet resistance was measured by encapsulating the transparent electrode with sodalime glass having a thickness of 700 탆, and the light transmittance was measured by measuring the transmittance of light having a wavelength of 550 nm.

The sheet resistance of the transparent electrode measured in Example 2 was 20? / ?, and the light transmittance was 51%.

≪ Example 3 > - Surface resistance and light transmittance

A first organic layer made of a compound represented by the above formula (1-1) and a metal layer made of Ag having a thickness of 10 nm were sequentially laminated on a sodalime glass having a thickness of 700 탆 to form a transparent electrode Respectively. The sheet resistance was measured by encapsulating the transparent electrode with sodalime glass having a thickness of 700 탆, and the light transmittance was measured by measuring the transmittance of light having a wavelength of 550 nm.

The sheet resistance of the transparent electrode measured in Example 3 was 8 Ω / □ and the light transmittance was 53%.

≪ Example 4 > - Surface resistance and light transmittance

A first organic layer made of the compound represented by Formula 1-1, a metal layer made of Ag having a thickness of 5 nm, and a metal layer made of Ag having a thickness of 20 nm were formed on sodalime glass having a thickness of 700 mu m, -1 > were sequentially laminated to form a transparent electrode. The sheet resistance was measured by encapsulating the transparent electrode with sodalime glass having a thickness of 700 탆, and the light transmittance was measured by measuring the transmittance of light having a wavelength of 550 nm.

The sheet resistance of the transparent electrode measured in Example 4 was 75 Ω / □ and the light transmittance was 63%.

≪ Example 5 > - Surface resistance and light transmittance

A first organic layer made of the compound represented by Formula 1-1, a metal layer made of Ag having a thickness of 7 nm and a metal layer made of Ag having a thickness of 30 nm were formed on sodalime glass having a thickness of 700 mu m, -1 > were sequentially laminated to form a transparent electrode. The sheet resistance and light transmittance were measured by encapsulating the transparent electrode with sodalime glass having a thickness of 700 mu m.

The sheet resistance of the transparent electrode measured in Example 5 was 20? / ?, and the light transmittance was 65%.

≪ Example 6 > - Sheet resistance and light transmittance

A first organic layer made of the compound represented by the above formula (1-1), a metal layer made of Ag having a thickness of 10 nm and a metal layer made of Ag having a thickness of 20 nm were formed on sodalime glass having a thickness of 700 mu m, -1 > were sequentially laminated to form a transparent electrode. The sheet resistance and light transmittance were measured by encapsulating the transparent electrode with sodalime glass having a thickness of 700 mu m.

The sheet resistance of the transparent electrode measured in Example 6 was 8? / ?, and the light transmittance was 59%.

≪ Comparative Example 1 > - Surface resistance and light transmittance

The sheet resistance and light transmittance were measured in the same manner as in Example 1, except that a transparent electrode was formed with a thickness of 15 nm as a transparent electrode.

The sheet resistance of the transparent electrode measured in Comparative Example 1 was 5,000? / ?, and the light transmittance was 42%.

≪ Comparative Example 2 > - Surface resistance and light transmittance

The sheet resistance and light transmittance were measured in the same manner as in Example 1, except that a transparent electrode was formed to a thickness of 20 nm as a transparent electrode.

The sheet resistance of the transparent electrode measured in Comparative Example 2 was 196? / ?, and the light transmittance was 39%.

≪ Comparative Example 3 > - Surface resistance and light transmittance

The sheet resistance and light transmittance were measured in the same manner as in Example 1, except that a transparent electrode was formed with a thickness of 25 nm as a transparent electrode.

The sheet resistance of the transparent electrode measured in Comparative Example 3 was 60 Ω / □, and the light transmittance was 29%.

≪ Comparative Example 4 > - Surface resistance and light transmittance

The sheet resistance and light transmittance were measured in the same manner as in Example 1, except that a transparent electrode was formed to a thickness of 15 nm using a 9: 1 weight ratio alloy of Yb and Ag as a transparent electrode.

The sheet resistance of the transparent electrode measured in Comparative Example 4 was 160 Ω / □, and the light transmittance was 44%.

≪ Comparative Example 5 > - Surface resistance and light transmittance

The sheet resistance and light transmittance were measured in the same manner as in Example 1, except that a transparent electrode was formed to a thickness of 20 nm using an alloy of Yb and Ag in a weight ratio of 9: 1 as a transparent electrode.

The sheet resistance of the transparent electrode measured in Comparative Example 5 was 100 Ω / □, and the light transmittance was 33%.

≪ Comparative Example 6 > - Surface resistance and light transmittance

The sheet resistance and light transmittance were measured in the same manner as in Example 1, except that a transparent electrode was formed to a thickness of 25 nm using a 9: 1 weight ratio alloy of Yb and Ag as a transparent electrode.

The sheet resistance of the transparent electrode measured in Comparative Example 6 was 74 Ω / □, and the light transmittance was 27%.

≪ Comparative Example 7 > - Surface resistance and light transmittance

The sheet resistance and light transmittance were measured in the same manner as in Example 1, except that a transparent electrode was formed to a thickness of 5 nm as a transparent electrode.

The sheet resistance of the transparent electrode measured in Comparative Example 7 was not measurable, and the light transmittance was 36%.

FIG. 11 shows a TEM image of the electrode prepared according to Comparative Example 7. FIG.

≪ Comparative Example 8 > - Sheet resistance and light transmittance

The sheet resistance and light transmittance were measured in the same manner as in Example 1, except that a transparent electrode was formed to a thickness of 10 nm as a transparent electrode.

The sheet resistance of the transparent electrode measured in Comparative Example 8 was 200? / ?, and the light transmittance was 27%.

FIG. 12 shows TEM images of the electrode prepared according to Comparative Example 8. FIG.

≪ Comparative Example 9 > - Sheet resistance and light transmittance

The sheet resistance and light transmittance were measured in the same manner as in Example 1, except that a transparent electrode was formed to a thickness of 20 nm as a transparent electrode.

The sheet resistance of the transparent electrode measured in Comparative Example 9 was 2? / ?, and the light transmittance was 23%.

≪ Comparative Example 10 > - Surface resistance and light transmittance

As in Example 1, except that a transparent electrode was formed by sequentially laminating a 5 nm metal layer made of Ag and a 20 nm organic material layer made of the compound represented by Chemical Formula 2 as a transparent electrode as the transparent electrode, the sheet resistance and the light transmittance Were measured.

The sheet resistance of the transparent electrode measured in Comparative Example 10 was 170 Ω / □, and the light transmittance was 37%.

FIG. 9 shows a TEM image of the electrode prepared according to Comparative Example 10. FIG.

≪ Comparative Example 11 > - Sheet resistance and light transmittance

As in Example 1, except that a transparent electrode was formed by sequentially laminating a 7 nm metal layer made of Ag and a 20 nm organic layer made of the compound represented by Chemical Formula 2 as a transparent electrode as a transparent electrode, the sheet resistance and light transmittance Were measured.

The sheet resistance of the transparent electrode measured in Comparative Example 11 was 100? / ?, and the light transmittance was 41%.

≪ Comparative Example 12 > - Sheet resistance and light transmittance

As in Example 1, except that a transparent electrode was formed by sequentially laminating a 10 nm metal layer made of Ag and a 20 nm organic material layer made of the compound represented by Chemical Formula 2 as a transparent electrode as a transparent electrode, the sheet resistance and light transmittance Were measured.

The sheet resistance of the transparent electrode measured in Comparative Example 12 was 70? / ?, and the light transmittance was 41%.

FIG. 10 shows a TEM image of the electrode prepared according to Comparative Example 12. FIG.

≪ Comparative Example 13 > - Surface resistance and light transmittance

The sheet resistance and light transmittance were measured in the same manner as in Example 1, except that a transparent electrode was formed as a transparent electrode with a thickness of 100 nm.

The sheet resistance of the transparent electrode measured in Comparative Example 13 was 43? / ?, and the light transmittance was 75%.

≪ Comparative Example 14 > - Surface resistance and light transmittance

The sheet resistance and light transmittance were measured in the same manner as in Example 1, except that a transparent electrode was formed as a transparent electrode with a thickness of 200 nm.

The sheet resistance of the transparent electrode measured in Comparative Example 14 was 21? / ?, and the light transmittance was 66%.

≪ Example 7 > - Performance evaluation of organic light emitting device

A substrate, a 20 nm first organic layer made of the compound represented by Formula 1-1, a 7 nm metallic layer made of Ag, and a 30 nm second organic layer made of the compound represented by Formula 1-1 are sequentially A hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an upper electrode were sequentially laminated.

≪ Example 8 > - Performance evaluation of organic light emitting device

A substrate, a 20 nm first organic layer made of the compound represented by Formula 1-1, a 12 nm metallic layer made of Ag, and a 30 nm second organic layer made of the compound represented by Formula 1-1 in sequence A hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an upper electrode were sequentially laminated.

≪ Example 9 > - Performance evaluation of organic light emitting device

Substrate, a 20 nm first organic layer made of the compound represented by Formula 1-1, a 15 nm metal layer made of Ag, and a 30 nm second organic layer made of the compound represented by Formula 1-1 are sequentially A hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an upper electrode were sequentially laminated.

≪ Comparative Example 15 > - Performance evaluation of organic light emitting device

An organic light emitting device was prepared in the same manner as in Example 7 except that ITO was formed to a thickness of 15 nm as a lower electrode.

The performance of the organic light emitting devices according to Examples 7 to 9 and Comparative Example 15 was compared in Table 1 below.

@ 3 mA / cm ² Bias
(V) CE
(cd / A) PE
(lm / W) Ext.QE
(%) Example 7 2.81 74.2 91.6 24.1 Example 8 2.78 85.0 113.3 27.7 Example 9 2.78 85.0 113.3 27.7 Comparative Example 15 2.89 63.1 72.9 20.4

In Table 1, Bias means the same as the operation voltage, and C.E. (Current efficiency) means the luminance emitted per unit current density, PE (Power efficacy), which means the luminous flux per unit of watt, and Ext.QE (External quantum efficiency) is the external quantum efficiency, And it can represent the absolute efficiency of the organic light emitting device.

As can be seen from the above Table 1, Examples 7 to 9 of this embodiment show that the operating voltage is low, the brightness and the brightness are high, and the efficiency is also higher than that of Comparative Example 15 in which ITO is applied as the lower electrode .

The J-V characteristic data of the organic light emitting devices according to Examples 7 to 9 and Comparative Example 15 are shown in Fig.

As can be seen from FIG. 15, the current density curve of the organic light emitting device according to the embodiment compared to the organic light emitting device according to the comparative example 15 is higher than that of the comparative example 15, which means that the charge injection characteristic is superior to the comparative example 15. This is because the driving voltage is driven by a voltage lower than the same luminance by a decrease of 0.1 V, And < RTI ID = 0.0 > C. < / RTI > In addition, it may be advantageous to optically optimize the organic light emitting diode by controlling the thickness of the first organic material layer and the second organic material layer.

Further, the lifetime-related data of the organic light emitting devices according to Examples 7 to 9 and Comparative Example 15 are shown in Fig.

As can be seen from FIG. 16, in Examples 7 to 9 of this embodiment, it can be seen that the low driving voltage and the high luminance are maintained for a long time, as compared with Comparative Example 15 in which ITO is applied as the lower electrode.

101, 102: first organic layer
201, 202: metal layer
301: second organic layer
401: inorganic layer

Claims (21)

A lower electrode; An upper electrode facing the lower electrode; And an organic layer disposed between the lower electrode and the upper electrode,
Wherein the lower electrode comprises a first organic compound layer comprising a compound represented by Formula 1 below; And a transparent electrode comprising one or more conductive units including a metal layer disposed in contact with the first organic material layer,
Wherein the metal layer is formed by depositing metal particles on the first organic material layer,
The first organic layer serves as a seed layer when depositing the metal particles,
Wherein the metal particles are Ag;
[Chemical Formula 1]

Each of R1 to R6 is hydrogen; A halogen group; Nitrile group (-CN); A nitro group (-NO ₂ ); A sulfonyl group (-SO ₂ R); Sulfoxide group (-SOR); A sulfonamide group (-SO ₂ NR _2); Sulfonate groups (-SO ₃ R); A trifluoromethyl group (-CF _3); Ester group (-COOR); An amide group (-CONHR or -CONRR '); A substituted or unsubstituted straight or branched chain C1 to C12 alkoxy group; A substituted or unsubstituted straight or branched chain C1 to C12 alkyl group; A substituted or unsubstituted straight or branched chain C2 to C12 alkenyl group; A substituted or unsubstituted aromatic or non-aromatic heterocyclic group; A substituted or unsubstituted aryl group; A substituted or unsubstituted mono- or di-arylamine group; And a substituted or unsubstituted aralkylamine group,
R and R 'are each a substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted 5- to 7-membered aliphatic cyclic group. The method according to claim 1,
Wherein the thickness of the first organic material layer is 5 nm or more and 50 nm or less. The method according to claim 1,
Wherein the thickness of the metal layer is 1 nm or more and 20 nm or less. The method according to claim 1,
And the light transmittance of the transparent electrode is 40% or more and 80% or less. The method according to claim 1,
Wherein each of R1 to R6 is a nitrile group (-CN). The method according to claim 1,
Wherein the compound represented by Formula 1 is any one of the following Formulas 1-1 to 1-6:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

The method according to claim 1,
Wherein the transparent electrode has one conductivity unit. The method according to claim 1,
Wherein the transparent electrode is formed by sequentially laminating two or more conductive units. The method according to claim 1,
Wherein the transparent electrode is provided in contact with the substrate, and the conductive unit in contact with the substrate is provided with the first organic material layer on the substrate. delete The method according to claim 1,
Wherein the metal layer includes one or more selected from the group consisting of a metal having a work function of 2 eV or more and 6 eV or less and an alloy of two or more thereof. The method of claim 11,
Wherein the metal having a work function of 2 eV or more and 6 eV or less is Au, Ag, Al, Ca, Mg, Yb, Sm, Cs, Ba, Li, Rb, Cu, Sn or Pt. delete The method according to claim 1,
And a second organic or inorganic layer on the conductive unit. 15. The method of claim 14,
Wherein the second organic material layer comprises a compound represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

Each of R1 to R6 is hydrogen; A halogen group; Nitrile group (-CN); A nitro group (-NO ₂ ); A sulfonyl group (-SO ₂ R); Sulfoxide group (-SOR); A sulfonamide group (-SO ₂ NR _2); Sulfonate groups (-SO ₃ R); A trifluoromethyl group (-CF _3); Ester group (-COOR); An amide group (-CONHR or -CONRR '); A substituted or unsubstituted straight or branched chain C1 to C12 alkoxy group; A substituted or unsubstituted straight or branched chain C1 to C12 alkyl group; A substituted or unsubstituted straight or branched chain C2 to C12 alkenyl group; A substituted or unsubstituted aromatic or non-aromatic heterocyclic group; A substituted or unsubstituted aryl group; A substituted or unsubstituted mono- or di-arylamine group; And a substituted or unsubstituted aralkylamine group,
R and R 'are each a substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted 5- to 7-membered aliphatic cyclic group. 15. The method of claim 14,
The inorganic layer may include ITO; IZO; IZTO; ATO; AZO; GZO; FTO; ZTO; ZnO; FZO; IGZO; WO ₃ ; ZrO _3; V ₂ O ₇ ; MoO ₃ ; Or ReO < _{3 &} gt ;. 15. The method of claim 14,
The transparent electrode has one conductive unit,
And the second organic material layer or the inorganic material layer is provided on the metal layer. 15. The method of claim 14,
Wherein the transparent electrode is formed by sequentially laminating two conductive units,
Wherein the second organic material layer or the inorganic material layer is provided on the metal layer of the conductive unit disposed closest to the upper electrode. 15. The method of claim 14,
Wherein the thickness of the second organic material layer or the inorganic material layer is 10 nm or more and 200 nm or less. The method according to claim 1,
And the sheet resistance value of the transparent electrode is 2? /? To 100? /?. The method according to claim 1,
Wherein the organic electronic device is an organic light emitting device, an organic solar cell, or an organic transistor.

Images