WO2010110034A1 - Organic el element - Google Patents

Abstract

Disclosed is an organic EL element which can have a prolonged service life. Specifically disclosed is an organic EL element which is characterized by comprising an anode, a cathode and a functional layer that is laminated between the anode and the cathode and comprises at least a hole-injection/transport layer, an organic light-emitting layer and an electron-transport layer, wherein the ratio of the thickness of the electron-transport layer to the total thickness of the anode and the hole-injection/transport layer [i.e., a (thickness of the electron-transport layer)/(total thickness of the anode and the hole-injection/transport layer) ratio] is 0.07 or more. The organic EL element is also characterized in that the ratio of the hole mobility of a hole-transporting material that constitutes the hole-injection/transport layer to the electron mobility of an electron-transporting material that constitutes the electron-transport layer [i.e., a (hole mobility of the hole-transporting material)/(electron mobility of the electron-transporting material) ratio] is 10 or more.

Description

Organic EL device

The present invention relates to an organic EL (electroluminescence) element, and particularly relates to extending the life of the organic EL element.

Conventionally, an organic EL element which is a self-luminous element formed of an organic material is, for example, a first electrode made of ITO (Indium Tin Oxide) or the like serving as an anode, an organic layer having at least a light emitting layer, and aluminum serving as a cathode. There is known one in which the organic EL element is formed by sequentially laminating a non-translucent second electrode made of (Al) or the like (for example, see Patent Document 1).

Such an organic EL device emits light by injecting holes from the first electrode and injecting electrons from the second electrode, and the holes and electrons recombine in the light emitting layer. An organic EL display using an organic EL element is applied to an in-vehicle display device such as a vehicle meter that requires instantaneous reading of a display because it has excellent visibility and responsiveness in a low temperature environment.

JP 59-194393 A

However, there is room for further improvement in that an organic EL display used in an in-vehicle display device is used for a long period of time and a long life is required.

Therefore, the present invention has been made in view of this problem, and an object thereof is to provide an organic EL element capable of extending the lifetime.

In order to solve the above-described problems, the present invention provides an organic EL device in which a functional layer having at least a hole injecting and transporting layer, an organic light emitting layer, and an electron transporting layer is laminated between an anode and a cathode. The ratio of the film thickness of the electron transport layer to the total film thickness of the anode and the hole injection transport layer (film thickness of the electron transport layer / total film thickness of the anode and the hole injection transport layer) Is 0.07 or more.

Further, the ratio of the hole mobility of the hole transporting material constituting the hole injecting and transporting layer to the electron mobility of the electron transporting material constituting the electron transporting layer (the hole of the hole transporting material). (Mobility / electron mobility of the electron transporting material) is 10 or more.

The total film thickness from the anode to the functional layer is 200 nm or less.

Further, the total film thickness from the anode to the functional layer is 170 nm or less.

Also, it is characterized by showing white light emission.

Further, a plurality of light emitting layers having different light emitting colors are formed as the organic light emitting layer, and white light emission is exhibited by color mixture.

The present invention relates to an organic EL element and can extend its life.

The figure which shows the organic electroluminescent panel to which this invention was applied. The expanded sectional view which shows the organic layer same as the above. The figure which shows the measurement result which compared the Example of this invention with the prior art example.

Hereinafter, embodiments in which the present invention is applied to a dot matrix type organic EL panel will be described with reference to the accompanying drawings.

In FIG. 1, the organic EL panel includes a support substrate 1, a first electrode (anode) 2, an insulating layer 3, a partition wall 4, a functional layer 5, a second electrode (cathode) 6, and a sealing member. 7 is mainly composed.

The support substrate 1 is a translucent glass substrate having a rectangular shape.

The first electrode 2 is formed of a light-transmitting conductive material such as ITO (Indium Tin Oxide) in a layer form on the support substrate 1 by a method such as sputtering or vapor deposition, and is patterned in a stripe pattern by a photolithography method, for example. It is made. As shown in FIG. 1A, the first electrode 2 has an anode wiring portion 2a and an anode portion 2b. The anode wiring portion 2a is an anode terminal portion for electrically connecting to an external power source at a terminal portion. 2c. The surface of the first electrode 2 is subjected to a surface treatment such as a plasma treatment.

The insulating layer 3 is made of an insulating material such as polyimide or phenol, and is formed in a predetermined shape on a non-light emitting portion on the support substrate 1 by means such as photolithography. The insulating layer 3 is formed between the anode portions 2 b of the first electrode 2 and is formed so as to slightly overlap the first electrode 2 and insulates the first electrode 2 from the second electrode 6. is there.

The partition wall portion 4 is made of, for example, an insulating material such as phenol, and has a cross section formed in, for example, a reverse taper shape by means such as photolithography. The partition wall portion 4 is formed on the first electrode 2 and the insulating layer 3 so as to intersect the anode portion 2b at a substantially right angle, and in the portion corresponding to the cathode wiring portion described later on the support substrate 1, FIG. ), The support substrate 1 is formed to have an arc shape when viewed from the laminated body forming surface side.

The functional layer 5 is formed on the first electrode 2 and the insulating layer 3, and as shown in FIG. 2, the hole injection transport layer 5a, the first light emitting layer (organic light emitting layer) 5b, the second The light emitting layer (organic light emitting layer) 5c, the electron transport layer 5d and the electron injection layer 5e are sequentially laminated by means such as vapor deposition to form a layer having a thickness of about 60 to 100 nm.

The hole injecting and transporting layer 5a has a function of taking holes from the first electrode 2 and transmitting them to the first and second light emitting layers 5b and 5c. For example, a hole having a high hole mobility such as an amine compound. The transporting material is formed in a layer form having a film thickness of about 15 to 40 nm by means such as vapor deposition. The hole transporting material has a glass transition temperature of 85 ° C. or higher (more preferably 130 ° C. or higher), a hole mobility of about 4 × 10 ⁻⁴ cm ² / V · s, and an energy gap of 3 About 1 eV.

The first light-emitting layer 5b is formed by doping a host material 5f with a first dopant 5g as a guest material by means such as a vapor deposition method to form a layer having a thickness of about 15 to 20 nm. The host material 5f is capable of transporting holes and electrons, and is made of a light-emitting material that emits light when the holes and electrons are transported and recombined. For example, an anthracene derivative having an energy gap of about 3.3 eV Consists of. The first dopant 5g has a function of emitting light in response to recombination of electrons and holes, and is made of a fluorescent dopant that exhibits a predetermined emission color, such as orange emission. It should be noted that the doping amount of the first dopant 5g is preferably set so as not to cause concentration quenching. In the present embodiment, the concentration in the first light emitting layer 5b is 2 to 20%. A first dopant 5g is added.

The second light emitting layer 5c is doped with the same host material 5f as the first light emitting layer 5b as a guest material with a second dopant 5h having a light emission color different from that of the first dopant 5g by means such as vapor deposition. It is formed in a layer shape with a film thickness of about 20 to 40 nm. The second dopant 5h has a function of emitting light in response to recombination of electrons and holes, and includes a predetermined dopant color, for example, a fluorescent dopant that emits blue light. It should be noted that the doping amount of the second dopant 5h is preferably set so as not to cause concentration quenching. In the present embodiment, the concentration in the second light emitting layer 5c is 2 to 20%. A second dopant 5h is added.

The electron transport layer 5d has a function of transmitting electrons to the second light-emitting layer 5c. For example, an electron transport material such as aluminum quinolinol (Alq ₃ ), which is a chelate compound, has a thickness of 8 It is formed in a layer of about 30 nm. Alternatively, an organic material having an electron mobility of 1 × 10 ⁻⁶ cm ² / V · s or less is used.

The electron injection layer 5e has a function of injecting electrons from the second electrode 6. For example, lithium fluoride (LiF) is formed into a layer having a thickness of about 0.5 nm by means of a vapor deposition method or the like.

The second electrode 6 is formed by forming a conductive material such as aluminum (Al) or magnesium silver (Mg: Ag) into a layer having a film thickness of about 50 to 200 nm by means such as vapor deposition. As a result, the arcuate cathode wiring portion 6a and the cathode portion 6b that intersects the transparent electrode 2 substantially at right angles are formed (see FIG. 1A). Further, the cathode wiring portion 6 a is electrically connected to the connection wiring portion 8. The connection wiring portion 8a is formed together with the first electrode 2, and is made of the same material ITO. Further, the connection wiring portion 8 is formed with a cathode terminal portion 8a for electrical connection with the external power source at the terminal portion.

As described above, the first electrode 2, the insulating layer 3, the partition wall 4, the functional layer 5, and the second electrode 6 are sequentially stacked on the support substrate 1 to form a stacked body. Opposite (crossing) portions of the anode portion 2b and the cathode portion 6b provided in a matrix form a light emitting pixel (organic EL element).

The sealing member 7 is formed by forming a molded glass or flat plate member made of a glass material into a concave shape by an appropriate method such as sand blasting, cutting, and etching. The sealing member 7 is hermetically disposed on the support substrate 1 via an adhesive 7a made of, for example, an ultraviolet curable epoxy resin, so that the laminate is sealed between the sealing member 7 and the support substrate 1. To do. The sealing member 7 is configured to be slightly smaller than the support substrate 1 so that the anode terminal portion 2c of the first electrode 2 and the cathode terminal portion 8a connected to the second electrode 6 are exposed to the outside. The sealing member 7 may have a flat plate shape. In this case, the sealing member 7 is disposed on the support substrate 1 via a spacer.

As described above, a dot matrix type organic EL panel having a display unit composed of organic EL elements can be obtained. This organic EL panel obtains orange light emission and blue light emission by recombining holes from the first electrode 2 and electrons from the second electrode 6 in the first and second light emitting layers 5b and 5c. The white light is emitted from the first electrode 2 side by mixing these colors. In addition, the organic EL panel applies a constant current by selecting one of the plurality of anode portions 2b and the plurality of cathode portions 6b formed in a stripe shape, and the opposite portion of the selected anode portion 2b and cathode portion 6b. The light emitting pixels corresponding to the above are driven to emit light by so-called passive driving.

The inventor of the present application defines the ratio (T2 / T1) between the film thickness T2 of the electron transport layer 5d of the organic EL element and the total film thickness T1 of the first electrode 2 and the hole injection transport layer 5a. It has been found that it is possible to extend the life by suppressing the decrease in light emission luminance with the passage of time. That is, the organic EL element in this embodiment has a ratio (T2 / T1) of 0.07 or more of the film thickness T2 of the electron transport layer 5d and the total film thickness T1 from the first electrode 2 to the hole injection transport layer 5a. It is characterized by. Furthermore, the ratio (M1 / M2) of the hole mobility M1 of the hole transport material constituting the hole injection transport layer 5a and the electron mobility M2 of the electron transport material constituting the electron transport layer 5d is determined. It is characterized by being 10 or more.

According to the above configuration, it is possible to extend the life by suppressing a decrease in light emission luminance with the passage of light emission time. Further, by setting the total film thickness T from the first electrode 2 to the functional layer 5 to 200 nm or less (more desirably 170 nm or less), it is possible to suppress an increase in drive voltage in a low temperature environment and to reduce the breakdown voltage of the drive IC. The manufacturing cost can be reduced. In addition, when a driving IC equivalent to the conventional one is used, the light emission luminance can be increased.

The specific effects of the present invention will be described below with further examples. FIG. 3 shows the film thickness of each layer of Examples 1 to 3 and Comparative Example 1. Note that since the thickness of the electron injection layer 5e is set to about 0.5 nm in any of the examples, it is omitted without being included in the total thickness T as an error category. In Example 1, the thickness of the first electrode 2 is 75 nm, the thickness of the hole injection transport layer 5a of the functional layer 5 is 32 nm, the thickness of the first light emitting layer 5b is 15 nm, and the second light emitting layer 5c The organic EL panel includes a light-emitting pixel (organic EL element) having a thickness of 40 nm, a thickness T2 of the electron transport layer 5d of 8 nm, and a total thickness T of 170 nm. The ratio (T2 / T1) between the film thickness T2 (8 nm) of the electron transport layer 5d and the total film thickness T1 (107 nm) of the first electrode 2 and the hole injection transport layer 5a is 0.074. The hole transport material constituting the hole injection / transport layer 5a has a hole mobility M1 of 4 × 10 ⁻⁴ cm ² / V · s, and the electron transport material constituting the electron transport layer 5d. The electron mobility M2 is 1 × 10 ⁻⁶ cm ² / V · s, and the ratio (M1 / M2) between them is 400. Example 2 is an organic EL produced in the same manner as in Example 1 except that the thickness of the hole injection transport layer 5a is 30 nm, the thickness T2 of the electron transport layer 5d is 10 nm, and the total thickness T is 170 nm. It is a panel. The ratio (T2 / T1) between the film thickness T2 (10 nm) of the electron transport layer 5d and the total film thickness T1 (105 nm) of the first electrode 2 and the hole injection transport layer 5a is 0.095. In addition, Example 3 was formed in the same manner as Example 1 except that the thickness of the hole injection transport layer 5a was 15 nm, the thickness T2 of the electron transport layer 5d was 25 nm, and the total thickness T was 170 nm. It is an organic EL panel. The ratio (T2 / T1) between the film thickness T2 (25 nm) of the electron transport layer 5d and the total film thickness T1 (90 nm) of the first electrode 2 and the hole injection transport layer 5a is 0.277. Comparative Example 1 was prepared in the same manner as in Example 1 except that the film thickness of the hole injection transport layer 5a was 35 nm, the film thickness T2 of the electron transport layer 5d was 5 nm, and the total film thickness T was 170 nm. It is an organic EL panel. The ratio (T2 / T1) between the film thickness T2 (5 nm) of the electron transport layer 5d and the total film thickness T1 (110 nm) of the first electrode 2 and the hole injection transport layer 5a is 0.045.

FIG. 3 shows the measurement results of the time until the luminance is halved with respect to the initial luminance when the first to third embodiments and the comparative example 1 are DC-driven in an environment of 90 ° C. with an initial luminance of 30000 cd / m ^2. ing. From the results of this evaluation, Example 1 in which the ratio (T2 / T1) between the film thickness T2 of the electron transport layer 5d and the total film thickness T1 of the first electrode 2 and the hole injection transport layer 5a was 0.07 or more. With respect to -3, it is possible to extend the time until the brightness is reduced to half or more compared to Comparative Example 1. On the other hand, Comparative Example 1 in which the ratio (T2 / T1) of the film thickness T2 of the electron transport layer 5d to the total film thickness T1 of the first electrode 2 and the hole injection transport layer 5a is less than 0.07 is sufficient. Life has not been obtained. It is clear that the present invention has a sufficient effect also from the measurement result.

In Examples 1 to 3 and Comparative Example 1, both the hole mobility M1 of the hole transport material constituting the hole injection transport layer 5a and the electrons of the electron transport material constituting the electron transport layer 5d are used. Although the ratio (M1 / M2) to the mobility M2 was the same value (400), more preferably the hole mobility M1 of the hole transporting material constituting the hole injection transport layer 5a and the electron transport layer The ratio (M1 / M2) to the electron mobility M2 of the electron transporting material constituting 5d may be specified. This is because the carrier balance of the organic EL element is determined by the difference between the hole mobility M1 of the hole transporting material and the electron mobility M2 of the electron transporting material, and the center position of light emission is determined. When the electron mobility M2 of the electron transport material is equal to or greater than the hole mobility M1 of the hole transport material, electrons are present at the interface between the hole injection transport layer 5a and the first light emitting layer 5b. As a result of accumulation, electrons enter the hole injection transport layer 5a. Then, since the hole transporting material constituting the hole injecting and transporting layer 5a is weak against electrons, the material is deteriorated, the luminance is lowered quickly, and the lifetime is shortened. Therefore, at least the hole mobility M1 of the hole transport material must be larger than the electron mobility M2 of the electron transport material. Appropriate values should be at least an order of magnitude different. Accordingly, in the present invention, the ratio of the hole mobility M1 of the hole transport material constituting the hole injection transport layer 5a to the electron mobility M2 of the electron transport material constituting the electron transport layer 5d ( It was found that the effect of the present invention can be obtained more effectively if M1 / M2) is 10 or more.

Further, although the present embodiment is a dot matrix type organic EL panel, the present invention can also be applied to a segment type organic EL panel and can also be applied to active driving.

In the present embodiment, the hole injection / transport layer 5a is composed of a single layer. In the present invention, a hole injection layer and a hole transport layer are sequentially stacked to form a hole injection / transport layer. May be composed of a plurality of layers.

In this embodiment, the host material 5f of the first light emitting layer 5b is a single material. However, in the present invention, a configuration using a plurality of materials as the host material may be used. Similarly, the host material 5f of the second light emitting layer 5c may be configured to use a plurality of materials instead of a single material.

In the present embodiment, the first light emitting layer 5b is obtained by doping the host material 5f with a dopant 5g that emits orange light, and the second light emitting layer 5c is a second light emitting material that emits blue light on the host material 5f. Although the dopant 5h is doped, in the present invention, each dopant added to the host material may emit light in other emission colors.

Further, in the present embodiment, the electron transport layer 5d is constituted by a single layer, but in the present invention, it may be constituted by a plurality of layers.

In addition, in the present embodiment, the two light emitting layers 5b and 5c are stacked. However, in the present invention, an element structure that exhibits monochromatic light emission may be used with one organic light emitting layer.

The present invention is particularly suitable for organic EL elements that require high reliability under a wide range of temperature environments.

DESCRIPTION OF SYMBOLS 1 Support substrate 2 1st electrode 3 Insulating layer 5 Functional layer 5a Hole injection transport layer 5b 1st light emitting layer (organic light emitting layer)
5c Second light emitting layer (organic light emitting layer)
5d Electron transport layer 5e Electron injection layer 5f Host material 5g First dopant 5h Second dopant 6 Second electrode

Claims (6)

An organic EL element formed by laminating a functional layer having at least a hole injection transport layer, an organic light emitting layer, and an electron transport layer between an anode and a cathode,
The ratio of the thickness of the electron transport layer to the total thickness of the anode and the hole injection transport layer (the thickness of the electron transport layer / the total thickness of the anode and the hole injection transport layer) is An organic EL element characterized by being 0.07 or more. The ratio of the hole mobility of the hole transport material constituting the hole injection transport layer to the electron mobility of the electron transport material constituting the electron transport layer (the hole mobility of the hole transport material) 2. The organic EL device according to claim 1, wherein / electron mobility of the electron transporting material is 10 or more. 2. The organic EL element according to claim 1, wherein a total film thickness from the anode to the functional layer is 200 nm or less. 2. The organic EL element according to claim 1, wherein a total film thickness from the anode to the functional layer is 170 nm or less. The organic EL device according to claim 1, which emits white light. The organic EL element according to claim 1, wherein a plurality of light emitting layers having different emission colors are formed as the organic light emitting layer, and emits white light by color mixture.

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