KR20100071723A - Amine derivatives and organic light emitting diode device comprising the same - Google Patents

Abstract

PURPOSE: A new amine derivative which can be used for a hole injection layer or hole transport layer is provided to prevent deterioration of surface between hole injection layer or hole transport layer and light-emitting layer. CONSTITUTION: An amine derivative is denoted by chemical formula 1. In chemical formula 1, R1 and R2 are independently substituted or non-substituted aromatic ring group having carbon number 6-20. R1 and the R2 which is not substituted are independently aromatic ring group including phenyl, biphenyl, naphthyl, terphenyls, anthracene, phenanthrene, or pyrene. The substituted R2 and the R1 are independently alkyl, alkoxy, halogen or cyano group. The organic electro luminescence device comprises anode, hole implant layer, hole-transport layer, light-emitting layer, electron-transport layer, electron injection layer, and cathode.

Description

Amine Derivatives And Organic Light Emitting Diode Device Comprising The Same}

The present invention relates to an organic electroluminescent device, and more particularly to an organic electroluminescent device comprising a novel amine derivative.

Recently, the importance of flat panel displays (FPDs) has increased with the development of multimedia. In response to this, a variety of liquid crystal displays (LCDs), plasma display panels (PDPs), field emission displays (FEDs), organic light emitting devices (Organic Light Emitting Devices), etc. Flat panel displays have been put into practical use.

In particular, the organic light emitting device has a high response time with a response speed of 1 ms or less, low power consumption, and self-luminous light. In addition, there is no problem in viewing angle, which is advantageous as a moving image display medium regardless of the size of the device. In addition, low-temperature manufacturing is possible, and the manufacturing process is simple based on the existing semiconductor process technology has attracted attention as the next generation flat panel display device.

The organic light emitting device may have a structure in which an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially stacked. Therefore, holes supplied from the anode and electrons received from the cathode combine in the emission layer to form excitons, which are hole-electron pairs, and emit light by energy generated when the excitons return to the ground state.

However, in the conventional organic light emitting device, a material used as a hole injection layer and a hole transport layer has a hole transfer rate so fast that holes are collected between the light emitting layer and the hole transport layer, and when the electrons enter, excitons are formed and emit light. If the speed is too high, the light emission may occur at the interface between the hole transport layer and the light emitting layer, thereby lowering the luminous efficiency of the device.

The present invention provides an organic electroluminescent device capable of improving the luminous efficiency of an organic electroluminescent device by forming a hole injection layer or a hole transport layer with a novel amine derivative.

In order to achieve the above object, the amine derivative according to an embodiment of the present invention may be represented by the following formula (1).

[Formula 1]

Here, R1 and R2 may be each independently selected from an aromatic ring group having 6 to 20 carbon atoms, which may be substituted or unsubstituted.

The unsubstituted R1 and R2 may each independently be any one selected from the group of aromatic rings including phenyl, biphenyl, naphthyl, terphenyl, anthracene, phenanthrene, pyrene, and florancene.

The substituted R1 and R2 may each independently have a substituent selected from alkyl, alkoxy, halogen and cyano groups.

The substituted or unsubstituted R1 and R2 may be any one selected from those represented by Formula 2, each independently.

The amine derivative may be any one selected from materials shown below.

In addition, the organic light emitting device according to an embodiment of the present invention is an organic light emitting device including an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode, the hole injection layer and the electron At least one of the transport layers may comprise the amine derivative of claim 1.

At least one of the hole injection layer and the electron transport layer may be formed to a thickness of 1 to 150nm.

Accordingly, the amine derivative and the organic light emitting device including the same according to an embodiment of the present invention prevent the deterioration of the interface between the hole injection layer or the hole transport layer and the light emitting layer by controlling the movement speed of the holes, and thus the organic light emitting device. There is an advantage that can improve the luminous efficiency.

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

1 is a view showing an organic light emitting display device according to an embodiment of the present invention.

Referring to FIG. 1, an organic light emitting display device 100 according to an exemplary embodiment of the present invention includes an anode 110, a hole injection layer 120, a hole transport layer 130, a light emitting layer 140, and an electron transport layer 150. The electron injection layer 160 and the cathode 170 may be included.

The anode 110 may be any one of an indium tin oxide (ITO), indium zinc oxide (IZO), or zinc oxide (ZnO) having a high work function as an electrode for injecting holes. In addition, when the anode 110 is a reflective electrode, the anode 110 includes a reflective layer made of any one of aluminum (Al), silver (Ag), or nickel (Ni) under a layer made of any one of ITO, IZO, or ZnO. It may further include.

The hole injection layer 120 or the hole transport layer 130 may serve to facilitate the injection of holes from the anode 110 to the light emitting layer 140, and may include an amine derivative represented by the following formula (1) Can be.

[Formula 1]

Here, R1 and R2 may be each independently selected from an aromatic ring group having 6 to 20 carbon atoms, which may be substituted or unsubstituted.

Herein, the unsubstituted R1 and R2 may each independently be selected from an aromatic ring group including phenyl, biphenyl, naphthyl, terphenyl, anthracene, phenanthrene, pyrene, and florancene.

In addition, the substituted R1 and R2 may each independently have a substituent selected from alkyl, alkoxy, halogen and cyano groups.

The substituted or unsubstituted R1 and R2 may be any one selected from those represented by Formula 2, each independently.

[Formula 2]

The amine derivative may be any one selected from materials shown below.

The hole injection layer 120 or the hole transport layer 130 including the amine derivative may play a role of preventing excitons from forming and emitting light at the interface of the emission layer by controlling the movement speed of the holes. Accordingly, there is an advantage in that the interface of the light emitting layer is prevented from deterioration and thus the luminance and driving voltage characteristics of the organic light emitting display device can be improved.

The hole injection layer 120 or the hole transport layer 130 may have a thickness of 1 to 150 nm. In this case, when the thickness of the hole injection layer 120 is 1 nm or more, there is an advantage of preventing the hole injection characteristic from being lowered. If the thickness is 150 nm or less, the hole injection layer 120 is too thick to move holes. There is an advantage that can prevent the driving voltage required to increase.

The emission layer 140 may emit red (R), green (G), and blue (B), and may be formed of a phosphor or a fluorescent material.

When the light emitting layer 140 is red, it includes a host material including CBP (carbazole biphenyl) or mCP (1,3-bis (carbazol-9-yl), and PIQIr (acac) (bis (1-phenylisoquinoline) acetylacetonate Phosphorescent light containing a dopant comprising at least one selected from the group consisting of iridium), PQIr (acac) (bis (1-phenylquinoline) acetylacetonate iridium), PQIr (tris (1-phenylquinoline) iridium), and PtOEP (octaethylporphyrin platinum) It may be made of a material, and alternatively may be made of a fluorescent material including PBD: Eu (DBM) ₃ (Phen) or perylene, but is not limited thereto.

When the light emitting layer 140 is green, it may include a host material including CBP or mCP, and may be made of a phosphor including a dopant material including Ir (ppy) 3 (fac tris (2-phenylpyridine) iridium). Unlike this, Alq3 (tris (8-hydroxyquinolino) aluminum) may be formed of a fluorescent material including, but is not limited thereto.

When the light emitting layer 140 is blue, it may be made of a phosphor including a host material including CBP or mCP, and including a dopant material including (4,6-F ₂ ppy) ₂ Irpic. spiro-DPVBi, spiro-6P, distilbenzene (DSB), distriarylene (DSA), PFO-based polymer and may be composed of a fluorescent material including any one selected from the group consisting of PPV-based polymer, but is not limited thereto. .

The electron transport layer 150 serves to facilitate the transport of electrons, made of one or more selected from the group consisting of Alq3 (tris (8-hydroxyquinolino) aluminum), PBD, TAZ, spiro-PBD, BAlq and SAlq. But it is not limited thereto.

The thickness of the electron transport layer 150 may be 1 to 50nm. In this case, when the thickness of the electron transport layer 150 is 1 nm or more, there is an advantage of preventing the electron transport characteristics from being lowered. In order to prevent the driving voltage from rising, there is an advantage.

The electron injection layer 160 serves to facilitate the injection of electrons, and may be Alq3 (tris (8-hydroxyquinolino) aluminum), PBD, TAZ, spiro-PBD, BAlq or SAlq, but is not limited thereto.

The electron injection layer 160 may have a thickness of about 1 nm to about 50 nm. In this case, when the thickness of the electron injection layer 160 is 1 nm or more, there is an advantage that the electron injection characteristics may be prevented from being lowered. There is an advantage that can be prevented from increasing the driving voltage to improve.

The cathode 170 is an electron injection electrode, and may be made of magnesium (Mg), calcium (Ca), aluminum (Al), silver (Ag), or an alloy thereof. Here, the cathode 170 may be formed to a thickness thin enough to transmit light when the organic light emitting device is a front or double-sided light emitting structure, and reflect the light when the organic light emitting device is a rear light emitting structure. It can form thick enough.

Hereinafter, the synthesis examples of the amine derivative of the present invention and the organic electroluminescent device including the same will be described in detail in the following synthesis examples and examples. However, the following examples are merely to illustrate the present invention is not limited to the following examples.

Synthetic example

1) Synthesis method of 3-bromophenylcarbazole

Phenylcarbazole (5.0 g, 0.0204 mol) and N-boromosuccinimide (3.18 g, 0.0214 mol) were added to a two-necked round bottom flask, and the solvent was dissolved in 200 mL of dichloromethane and refluxed at room temperature for 24 hours. After the reaction was terminated and the solvent was removed, 200 mL of methanol was added and filtered to obtain 3-bromophenylcarbazole.

2) Synthesis of N-phenyl-N, N'-diphenylbenzidine

N.N'-diphenylbenzidine (3g, 0.0089mol), bromobenzene (2.8g, 0.018mol), 2,2'-bis (diphenylphosphino) -1,1'- in a two-neck round bottom flask Vinaphthyl (0.052 g, 1% mol), palladium (II) acetate (0.019 g, 1% mol) and sodium tert-butoxide (2.3 g, 0.029 mol) were dissolved in 80 mL of toluene and refluxed for 24 hours. After the reaction was completed, the round bottom flask was cooled, 30 mL of toluem, a reaction solvent was removed, and 150 mL of methanol was added thereto to obtain a precipitate. The precipitate was then filtered and recrystallized with dichloromethane and methanol to give N-phenyl-N, N'-diphenylbenzidine.

3) Synthesis method of HM-01

N-phenyl-N, N'-diphenylbenzidine (2.5 g, 0.006 mol), 3-bromophenylcarbazole (2.9 g, 0.009 mol), 2,2'-bis (diphenyl) in a two-necked round bottom flask 80 mL of toluene in phosphino) -1,1'-binafyl (0.052 g, 1% mol), palladium (II) acetate (0.019 g, 1% mol) and sodium tert-butoxide (2.8 g, 0.035 mol) It was dissolved in and refluxed for 30 hours. After the reaction was completed, the round bottom flask was cooled, 30 mL of toluene, a reaction solvent was removed, and 150 mL of methanol was added thereto to obtain a precipitate. Subsequently, the precipitate was filtered and recrystallized with dichloromethane and methanol to obtain an amine derivative represented by HM-01.

Example

Hereinafter, an embodiment in which an organic light emitting display device is manufactured using the amine derivative of the present invention represented by the aforementioned HM-01, 03, 12, 15, 16, 23 as a hole transport layer will be described.

≪ Example 1 >

The light emitting area of the ITO glass was patterned to have a size of 2 mm x 2 mm and then washed. After mounting the substrate in the vacuum chamber, the base pressure was 1 × 10 ^-6 torr, and the hole injection layer DNTPD was deposited to a thickness of 650 kPa on the anode ITO, and the HM-01 material, the hole transport layer, was deposited to a thickness of 400 kPa. And ADN (9,10-di (2-naphthyl) anthracene) and GD-1 (10- (2-benzothiazolyl) -1,1,7,7-tetramethyl-2,, 3,6, 250-Hz green light-emitting layer was formed by using 7-tetrahydro-1H, 5H, 11H- [I] benzo-pyrano [6,7,8-ij]) as a host and a dopant, respectively. At this time, the doping concentration was 2%. Then, Alq ₃ as an electron transport layer was formed to a thickness of 350 kW, LiF as an electron injection layer was formed to a thickness of 5 kW, and Al as a cathode was formed to a thickness of 1000 kW to produce an organic light emitting device.

<Example 2>

Under the same conditions as in Example 1, an organic light emitting display device was manufactured by using a different hole transport layer with an amine derivative represented by HM-03.

<Example 3>

Under the same conditions as in Example 1, an organic light emitting display device was manufactured by changing a hole transport layer using an amine derivative represented by HM-012.

<Example 4>

Under the same conditions as in Example 1, an organic light emitting display device was manufactured by changing a hole transport layer using an amine derivative represented by HM-15.

Example 5

Under the same conditions as in Example 1, an organic light emitting display device was manufactured by using a hole transport layer with an amine derivative represented by HM-16.

<Example 6>

Under the same conditions as in Example 1, an organic light emitting display device was manufactured by using a different hole transport layer with an amine derivative represented by HM-23.

Comparative Example

Under the same conditions as in Example 1, the organic light emitting diode was manufactured by using only the hole transport layer made of NPD.

The current density, luminance, driving voltage and color coordinates of the organic light emitting diodes manufactured according to Examples 1 to 6 and Comparative Examples were measured and shown in Table 1 below. In addition, the emission spectrum of the organic light emitting display device manufactured according to Example 1 was measured and shown in FIG. 2.

Current density
(mA㎠) Luminance
(cd / ㎡) Driving voltage
(V) Color coordinates CIE (X) CIE (Y) Example 1 10 1495 7.0 0.318 0.599 Example 2 10 1515 6.8 0.317 0.600 Example 3 10 1483 6.9 0.318 0.598 Example 4 10 1523 6.8 0.318 0.599 Example 5 10 1521 7.0 0.318 0.599 Example 6 10 1498 7.2 0.317 0.598 Comparative example 10 1350 7.3 0.318 0.588

As shown in Table 1, it can be seen that the organic light emitting display device manufactured according to Examples 1 to 6 exhibits color coordinates according to the comparative example, while the brightness of the organic light emitting display device is significantly higher than that of the comparative example. It can be seen that the improved, and the driving voltage is lower than the comparative example.

And, as shown in Figure 2, it can be seen that the peak appears accurately in the green wavelength band and the intensity is also high.

Therefore, the amine derivative and the organic light emitting device including the same according to an embodiment of the present invention have an advantage of improving the luminance and driving voltage characteristics compared to the conventional organic light emitting device.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be practiced. Therefore, the embodiments described above are to be understood as illustrative and not restrictive in all aspects. In addition, the scope of the present invention is shown by the claims below, rather than the above detailed description. Also, it is to be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts are included in the scope of the present invention.

1 is a view showing an organic light emitting display device according to an embodiment of the present invention.

2 is a light emission spectrum graph of an organic light emitting display device manufactured according to Experimental Example 1 of the present invention.

Claims (7)

An amine derivative represented by the following formula (1). [Formula 1]

Here, R1 and R2 may be each independently selected from an aromatic ring group having 6 to 20 carbon atoms, which may be substituted or unsubstituted. The method of claim 1, The unsubstituted R1 and R2 are each independently any one selected from an aromatic ring group including phenyl, biphenyl, naphthyl, terphenyl, anthracene, phenanthrene, pyrene, and florancene. The method of claim 1, The substituted R1 and R2 are each independently an amine derivative having any one selected from alkyl, alkoxy, halogen and cyano groups as substituents. The method of claim 1, The substituted or unsubstituted R1 and R2 are each independently any one selected from those represented by the following formula (2). [Formula 2]

The method of claim 1, The amine derivative is any one selected from the substances shown below.

In the organic light emitting device comprising an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode, At least one of the hole injection layer and the electron transport layer is an organic electroluminescent device comprising the amine derivative of claim 1. The method of claim 6, At least one of the hole injection layer and the electron transport layer is an organic light emitting device consisting of a thickness of 1 to 150nm.

Images