KR20120122931A - Light-emitting device, electronic device, and lighting device utilizing phosphorescence - Google Patents

Abstract

PURPOSE: An electroluminescence apparatus is provided to highly maintain brightness after 20 hours and to reduce consumption power because recombination efficiency becomes higher in an electroluminescence layer. CONSTITUTION: An electroluminescence apparatus comprises an electroluminescence diode and the electroluminescence element thereof comprises phosphor-emitting organic metal iridium complex which comprises iridium, and pyrimidine which comprises an aryl group in a fourth position. Nitrogen in a third position of the pyrimidine coordinates the iridium. The pyrimidine comprises an alkyl group or aryl group in one of a second position fifth position and sixth position. An ortho position of the aryl group combined to the fourth position of the pyrimidine is combined to the iridium. The electroluminescence device comprises an electroluminescent layer comprising the phosphor-emitting organic metal iridium complex between a pair of electrodes.

Description

Light emitting devices, electronic devices and lighting devices based on phosphorescence emission {LIGHT-EMITTING DEVICE, ELECTRONIC DEVICE, AND LIGHTING DEVICE UTILIZING PHOSPHORESCENCE}

One aspect of the present invention relates to a light emitting device based on phosphorescence emission. That is, the present invention relates to a light emitting device capable of obtaining phosphorescent light emission by providing a light emitting element having an EL layer containing an organometallic iridium complex capable of converting triplet excitation energy into light emission. The present invention also relates to electronic devices and lighting devices based on phosphorescence emission.

The organic compound enters an excited state by absorbing light. Through this excitation state, various reactions (photochemical reactions) or light emission (luminescence) can be caused, and various applications have been made.

As an example of photochemical reaction, there exists reaction (oxygen addition) of singlet oxygen with unsaturated organic molecule (for example, refer nonpatent literature 1). Since oxygen molecules are triplet states in the ground state, singlet oxygen (singlet oxygen) is not produced by direct photoexcitation. However, in the presence of other triplet excitation molecules, singlet oxygen can be produced to cause an oxygen addition reaction. At this time, a compound capable of forming triplet excitation molecules is called a photosensitizer.

As such, in order to generate singlet oxygen, a photosensitizer capable of forming triplet excitation molecules by photoexcitation is required. However, since conventional organic compounds have a singlet state in the ground state, photoexcitation to the triplet excited state becomes a forbidden transition, and triplet excitation molecules are difficult to form. Therefore, as such a photosensitizer, the compound which is easy to produce the crossover from the singlet excited state to the triplet excited state (or the compound which allows the prohibited transition photoexcited to the triplet excited state directly) is calculated | required. In other words, such a compound can be said to be useful because it can be used as a photosensitizer.

In addition, these compounds can often emit phosphorescence. Phosphorescence is luminescence generated by transitions between energies with different degrees of multiplicity. In conventional organic compounds, luminescence refers to luminescence generated when returning from the triplet excited state to the singlet ground state (in contrast to the singlet in the singlet excited state. Light emission upon return to the ground state is called fluorescence). As a field of application of a compound capable of emitting phosphorescence, that is, a compound capable of converting a triplet excited state into luminescence (hereinafter referred to as a phosphorescent compound), a light emitting device using an organic compound as a luminescent material may be mentioned.

This light emitting device has a simple structure in which a light emitting layer including an organic compound that is a light emitting material is provided between electrodes, and is attracting attention as a next-generation flat panel display device due to characteristics such as thin, light weight, high speed response, and direct current low voltage driving. In addition, the display using this light emitting element also has excellent contrast and image quality and a wide viewing angle.

The light emitting device of the light emitting element using the organic compound as the light emitting material is a carrier injection type. That is, by providing a light emitting layer between the electrodes and applying a voltage, electrons and holes injected through the electrodes recombine to emit light when the light emitting material is in an excited state and the excited state returns to the ground state. As the type of the excited state, the singlet excited state S ^* and the triplet excited state T ^* are possible as in the case of the optical excitation described above. In addition, the statistical generation ratio in the light emitting element is considered to be S ^* : T ^* = 1: 3.

Compounds that convert singlet excited states to luminescence (hereinafter referred to as fluorescent compounds) are not observed light emission from the triplet excited state (phosphorescence) at room temperature but only light emission from the singlet excited state (fluorescence). Therefore, the theoretical limit of the internal quantum efficiency (the ratio of photons generated to the injected carrier) in the light emitting device using the fluorescent compound is assumed to be 25% based on S ^* : T ^* = 1: 3.

On the other hand, when the above-mentioned phosphorescent compound is used, the internal quantum efficiency can theoretically be made up to 75 to 100%. That is, 3 to 4 times the luminous efficiency compared with a fluorescent compound is attained. For this reason, development of a light emitting device using a phosphorescent compound has been actively made in recent years in order to realize a high efficiency light emitting device (see, for example, Non-Patent Document 2). In particular, as a phosphorescent compound, the organometallic complex which uses iridium etc. as a center metal is attracting attention because of high phosphorescence quantum yield.

1. Haruo Inoue, three others, basic chemistry course photochemistry I (Maruzen), 106-110 2. Zhang, Guo-Lin, et al. 5, Gaodeng Xuexiao Huaxue Xuebao (2004), vol. 25, No. 3, 397-400

One object of the present invention is to provide a light emitting device based on phosphorescence emission. Another object of one embodiment of the present invention is to provide an electronic device and an illumination device based on phosphorescence emission.

In one embodiment of the present invention, nitrogen at the 3rd position of the pyrimidine having an aryl group at the 4th position is coordinated with iridium, and has an alkyl group or an aryl group at any of the 2nd, 5th and 6th positions of the pyrimidine, The aryl group at the fourth position is a light emitting device including a phosphorescent organometallic iridium complex having an ortho metallized structure by combining with iridium.

In addition, the phosphorescent organometallic iridium complex which has the said structure is a phosphorescent organometallic iridium complex which has a structure represented by the following general formula (G1).

(Wherein Ar represents a substituted or unsubstituted aryl group, and R ¹ to R ³ each independently represent hydrogen, a substituted or unsubstituted C 1-4 alkyl group, or a substituted or unsubstituted C 6-10 aryl group). And at least one of R ¹ to R ³ represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.)

In another embodiment of the present invention, nitrogen in the first position of 1, 3, 5-triazine having an aryl group in the second position is coordinated with iridium, and any of the 4th and 6th positions of 1, 3, 5-triazine is A light emitting device having a substituent on one, and an aryl group comprising a phosphorescent organometallic iridium complex having an ortho metallized structure by combining with an iridium.

In addition, the phosphorescent organometallic iridium complex which has the said structure is a phosphorescent organometallic iridium complex which has a structure represented by the following general formula (G2).

(Wherein Ar represents a substituted or unsubstituted aryl group, R ⁴ and R ⁵ each independently represent hydrogen, a substituted or unsubstituted C 1-4 alkyl group, a substituted or unsubstituted C 1-4 alkoxy group) , A substituted or unsubstituted C1-C4 alkylthio group, a halogen group, a substituted or unsubstituted C1-C4 haloalkyl group, or a substituted or unsubstituted C6-C10 aryl group Provided that at least one of R ⁴ to R ⁵ is a substituted or unsubstituted C 1-4 alkyl group, a substituted or unsubstituted C 1-4 alkoxy group, or a substituted or unsubstituted C 1-4 alkyl alkyl Or a halogen group, a substituted or unsubstituted haloalkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.)

In addition, the phosphorescent organometallic iridium complex having the structures represented by the formulas (G1) and (G2), in which the lowest triplet excited state is formed, is preferable since it can efficiently emit phosphorescence.

Here, as a phosphorescent organometallic iridium complex which has a structure represented by general formula (G1) mentioned above, specifically, the phosphorescent organometallic iridium complex represented by the following general formula (G3) is more preferable.

(Wherein Ar represents a substituted or unsubstituted aryl group, and R ¹ to R ³ each independently represent hydrogen, a substituted or unsubstituted C 1-4 alkyl group, or a substituted or unsubstituted C 6-10 aryl group). Provided that at least one of R ¹ to R ³ represents either a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. , L represents a monoanionic ligand.)

Moreover, as a phosphorescent organometallic iridium complex which has a structure represented by general formula (G2) mentioned above, specifically, the phosphorescent organometallic iridium complex represented by the following general formula (G4) is more preferable.

(Wherein Ar represents a substituted or unsubstituted aryl group, R ⁴ and R ⁵ each independently represent hydrogen, a substituted or unsubstituted C 1-4 alkyl group, a substituted or unsubstituted C 1-4 alkoxy group) , A substituted or unsubstituted C1-C4 alkylthio group, a halogen group, a substituted or unsubstituted C1-C4 haloalkyl group, or a substituted or unsubstituted C6-C10 aryl group. Provided that at least one of R ⁴ to R ⁵ is a substituted or unsubstituted C 1-4 alkyl group, a substituted or unsubstituted C 1-4 alkoxy group, a substituted or unsubstituted C 1-4 alkylthio group, A halogen group, a substituted or unsubstituted haloalkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and L represents a monoanionic ligand.)

In addition, in the aforementioned general formulas (G3) and (G4), the monoanionic ligand L is a monoanionic bidentate chelate ligand having a betadiketone structure, or a monoanionic bidentate chelate ligand having a carboxyl group, or a phenolic hydroxyl group. Preferred is either a monoanionic bidentate chelate ligand having or a monoanionic bidentate chelate ligand in which both coordination elements are nitrogen. Especially preferably, it is a monoanionic ligand shown to the following structural formula (L1)-(L7). These ligands are effective because of their high coordination ability and low availability.

(Wherein, R ² 1 to R ⁵⁸ are each independently hydrogen, a substituted or unsubstituted C 1-4 alkyl group, a halogen group, a vinyl group, a substituted or unsubstituted C 1-4 haloalkyl group, substituted or An unsubstituted alkoxy group having 1 to 4 carbon atoms or a substituted or unsubstituted alkylthio group having 1 to 4. In addition, each of A ¹ to A ⁴ independently represents sp ² hybrid carbon bonded to nitrogen and hydrogen, Or sp ² hybrid carbon bonded to substituent R, and substituent R represents an alkyl group having 1 to 4 carbon atoms, a halogen group, a haloalkyl group having 1 to 4 carbon atoms, or a phenyl group.)

Moreover, as a phosphorescent organometallic iridium complex which has a structure represented by general formula (G1) mentioned above, specifically, the phosphorescent organometallic iridium complex represented by the following general formula (G5) is more preferable.

(Wherein Ar represents a substituted or unsubstituted aryl group, and R ¹ to R ³ each independently represent hydrogen, a substituted or unsubstituted C 1-4 alkyl group, or a substituted or unsubstituted C 6-10 aryl group). And at least one of R ¹ to R ³ represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.)

Moreover, as a phosphorescent organometallic iridium complex which has a structure represented by general formula (G2) mentioned above, specifically, the phosphorescent organometallic iridium complex represented by the following general formula (G6) is more preferable.

(Wherein Ar represents a substituted or unsubstituted aryl group, R ⁴ and R ⁵ each independently represent hydrogen, a substituted or unsubstituted C 1-4 alkyl group, a substituted or unsubstituted C 1-4 alkoxy group) , A substituted or unsubstituted C1-C4 alkylthio group, a halogen group, a substituted or unsubstituted C1-C4 haloalkyl group, or a substituted or unsubstituted C6-C10 aryl group. Provided that at least one of R ⁴ to R ⁵ is a substituted or unsubstituted C 1-4 alkyl group, a substituted or unsubstituted C 1-4 alkoxy group, a substituted or unsubstituted C 1-4 alkylthio group, A halogen group, a substituted or unsubstituted haloalkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.)

Moreover, as a phosphorescent organometallic iridium complex which has a structure represented by general formula (G1)-(G6) mentioned above, specifically, the phosphorescent organometallic iridium complex represented by following structural formula (100)-(104) is more preferable. .

In addition, the above-mentioned phosphorescent organometallic iridium complex can emit phosphorescence, that is, it can convert triplet excitation energy into luminescence and exhibit luminescence. It is very effective because high efficiency is possible by applying.

A light emitting device according to another aspect of the present invention has a light emitting element formed by disposing an EL layer between a pair of electrodes. In addition, it is preferable that the light emitting layer contained in an EL layer is formed including the said phosphorescent organometallic iridium complex (guest material), a 1st organic compound, and a 2nd organic compound. In this case, for example, by selecting the electron trapping compound as the first organic compound and the hole trapping compound as the second organic compound, the recombination efficiency in the light emitting layer is increased and the power consumption can be reduced.

Alternatively, the light emitting layer included in the EL layer is formed including the phosphorescent organometallic iridium complex (guest material), the first organic compound, and the second organic compound, and the first organic compound and the second organic compound form an exciplex. It is preferable that it is a combination. This light emitting device can improve energy transfer efficiency by energy transfer using superposition of the emission spectrum of the exciplex and the absorption spectrum of the phosphorescent compound. Therefore, the light emitting device can be reduced in power consumption by being applied to a light emitting device.

That is, the light emitting device has an EL layer between a pair of electrodes, the EL layer contains a phosphorescent organometallic iridium complex, a first organic compound, and a second organic compound, and the phosphorescent organometallic iridium complex is 4 Nitrogen at position 3 of the pyrimidine having an aryl group is coordinated with iridium, and has an alkyl group or an aryl group at any of positions 2, 5 and 6 of pyrimidine, and the aryl group at position 4 of pyrimidine is bonded to iridium. Thus, the light emitting device has an ortho-metalized structure, and the first organic compound and the second organic compound form an exciplex.

Moreover, it has an EL layer between a pair of electrodes, an EL layer contains a phosphorescent organometallic iridium complex, a 1st organic compound, and a 2nd organic compound, and the phosphorescent organometallic iridium complex is 1 which has an aryl group in 2nd position. Nitrogen at the 1st position of the 3,5-triazine is coordinated to iridium, and has a substituent at any of the 4th and 6th positions of the 1,3,5-triazine, and the aryl group is bonded with iridium to ortho metallization The light emitting device having the structure of the present invention, wherein the first organic compound and the second organic compound form an exciplex, is also included in the above configuration.

Furthermore, the light-emitting device which is another aspect of this invention is the light emitting element by which the EL layer containing the said phosphorescent organometallic iridium complex is laminated | stacked by the charge generation layer between a pair of electrodes (so-called tandem type light emitting element). Has In addition, the tandem light emitting device can emit light in a high luminance region while maintaining a low current density. Since the current density can be kept low, a long-life element can be realized, and the low-voltage driving can be realized by applying the light emitting device to achieve low power consumption.

That is, the light emitting device has a plurality of EL layers between a pair of electrodes, and at least one layer (preferably one layer or more and three layers or less) of the plurality of EL layers is the third position of pyrimidine having an aryl group on the fourth position. Nitrogen is coordinated with iridium, has an alkyl group or an aryl group in any one of the 2nd, 5th and 6th positions of the pyrimidine, and the aryl group of 4th position of the pyrimidine is bonded to the iridium to form an ortho metallized structure A light emitting device comprising a phosphorescent organometallic iridium complex having a compound.

Further, a plurality of EL layers are provided between a pair of electrodes, and at least one layer (preferably one layer or more and three layers or less) of the plurality of EL layers is formed of 1, 3, 5-triazine having an aryl group in the second position. Nitrogen at the 1st position coordinates with iridium, has a substituent in any one of the 4th and 6th positions of said 1, 3, 5-triazine, and the electric aryl group bonds with the iridium, and has an ortho metallized structure A light emitting device comprising a sex organometallic iridium complex is also included in the above configuration.

In addition, in each of the above structures of a light emitting device including a tandem light emitting device, a structure in which phosphorescent light emission can be obtained from an EL layer containing a phosphorescent organometallic iridium complex, and a plurality of EL layers comprise a phosphorescent organometallic iridium complex. The structure which has at least 1 layer of EL layers which do not contain, Furthermore, the some EL layer is comprised by the phosphorescent organometallic iridium complex, and does not contain the EL layer which can obtain phosphorescence, and a phosphorescent organometallic iridium complex. In addition, the structure which has the EL layer which can acquire fluorescent light emission, respectively shall also be included in this invention.

A light emitting device according to another aspect of the present invention has a light emitting element formed by arranging an EL layer containing the phosphorescent organic metal iridium complex between a pair of electrodes. In addition, one electrode of the pair of electrodes is formed to function as a reflective electrode and the other electrode to function as a semi-transmissive semi-reflective electrode, and formed by adjusting the optical distance between the two electrodes so as to emit light having a different wavelength for each light emitting device do. By applying such a light emitting element to a light emitting device (so-called light emitting device of microcavity structure), the light emission intensity in the front direction of a specific wavelength can be enhanced, thereby achieving low power consumption. This configuration is particularly useful when applied to a color display (image display device) using pixels of three or more colors.

That is, the light emitting device includes a first light emitting element having a reflective electrode, a first transparent conductive layer formed in contact with the reflective electrode, an EL layer formed in contact with the first transparent conductive layer, and a semi-transmissive semi-reflective electrode formed in contact with the EL layer; A second light emitting element having an electrode, a second transparent conductive layer formed in contact with the reflective electrode, an EL layer formed in contact with the second transparent conductive layer, and a semi-transmissive semi-reflective electrode formed in contact with the EL layer, and formed in contact with the reflective electrode and the reflective electrode An EL layer and a third light emitting element having a semi-transmissive semi-reflective electrode formed in contact with the EL layer, wherein the EL layer has a third position of pyrimidine having an aryl group on the fourth position, coordinated with iridium, and a second position of pyrimidine. , An alkyl group or an aryl group in any of the 5th and 6th positions, and the aryl group of the 4th position of pyrimidine includes a phosphorescent organometallic iridium complex having an ortho metallized structure by combining with iridium, By setting the conductive layer and the second transparent conductive layer to a desired total thickness, light having a longer wavelength than that of the second light emitting device is emitted from the first light emitting device, and light having a longer wavelength than the third light emitting device is emitted from the second light emitting device. A light emitting device characterized in that the injection.

Further, a first light emitting element having a reflective electrode, a first transparent conductive layer formed in contact with the reflective electrode, an EL layer formed in contact with the first transparent conductive layer, and a semi-transmissive semi-reflective electrode formed in contact with the EL layer, a reflective electrode, and a reflective electrode A second light emitting element having a second transparent conductive layer formed in contact with the second transparent conductive layer, an EL layer formed in contact with the second transparent conductive layer and a semi-transmissive semi-reflective electrode formed in contact with the EL layer, an EL layer formed in contact with the reflective electrode and the reflective electrode, and an EL It has a 3rd light emitting element which has the semi-transmissive semi-reflective electrode formed in contact with a layer, The EL layer has nitrogen of the 1st position of 1, 3, 5-triazine which has an aryl group in 2nd, and coordinates to iridium, and 1, 3 And a substituent on any of the 4th and 6th positions of 5-triazine, and the aryl group includes a phosphorescent organometallic iridium complex having an orthometallized structure by bonding with iridium, the first transparent conductive layer and the second Each transparent transparent layer The light emitting device is characterized in that the total thickness of the light emitting device is emitted from the first light emitting device longer wavelength than the second light emitting device, the light emitted from the second light emitting device longer wavelength than the third light emitting device Included in

In addition, the light emitting device having the microcavity structure and the light emitting device configured in combination with the tandem light emitting device described above are also included in the present invention.

In addition, one aspect of the present invention includes not only a light emitting device having a light emitting element, but also an electronic device and a lighting device having the light emitting device in the category. Therefore, in the present specification, the light emitting device means an image display device, a light emitting device or a light source (including a lighting device). In addition, a module equipped with a connector, for example, a flexible printed circuit (FPC) or Tape Automated Bonding (TAB) tape or a tape carrier package (TCP), a module having a printed wiring board at the end of the TAB tape or TCP, or a light emitting device All modules in which ICs (integrated circuits) are directly mounted by a chip on glass (COG) method are to be included in the light emitting device.

One aspect of the present invention can provide a light emitting device based on phosphorescence emission. In addition, one aspect of the present invention can provide an electronic device and an illumination device based on phosphorescence emission.

1 is a view for explaining the structure of a light emitting element,
2 is a diagram for explaining the structure of a light emitting element;
3 is a view for explaining the structure of the light emitting element;
4 is a diagram for explaining a light emitting device;
5 is a view for explaining a light emitting device;
6 is a diagram for explaining an electronic device,
7 is a diagram for explaining a lighting device.
8 is a view for explaining a light emitting element,
9 is a view showing the luminance-current efficiency characteristics of Light-emitting Element 1,
10 is a view showing voltage-luminance characteristics of Light-emitting Element 1,
11 is a diagram showing an emission spectrum of Light-emitting Element 1,
12 is a ¹ H-NMR chart of the phosphorescent organometallic iridium complex of Structural Formula (100),
13 is a ¹ H-NMR chart of the phosphorescent organometallic iridium complex of Structural Formula (101),
14 is a ¹ H-NMR chart of the phosphorescent organometallic iridium complex of Structural Formula (102),
15 is a ¹ H-NMR chart of the phosphorescent organometallic iridium complex of Structural Formula (103),
16 is a view showing the luminance-current efficiency characteristics of Light-emitting Element 2,
17 is a view showing voltage-luminance characteristics of Light-emitting Element 2,
18 is a diagram showing an emission spectrum of Light-emitting Element 2,
19 is a view showing the reliability of the light emitting element 2,
20 is a diagram showing the luminance-current efficiency characteristics of Light-emitting Element 3,
21 is a view showing the voltage-luminance characteristics of Light-emitting Element 3,
22 is a diagram showing an emission spectrum of Light-emitting Element 3,
23 is a view showing the reliability of the light emitting element 3,
24 is a diagram showing the luminance-current efficiency characteristics of Light-emitting Element 4,
25 is a diagram illustrating voltage-luminance characteristics of Light-emitting Element 4,
26 is a diagram showing an emission spectrum of Light-emitting Element 4,
27 is a view showing the reliability of the light emitting element 4,
28 is a ¹ H-NMR chart of the phosphorescent organometallic iridium complex of Structural Formula (105),
29 is a ¹ H-NMR chart of 1,6mMemFLPAPrn (abbreviated);
30 is a diagram illustrating a light emitting element;
31 is an ultraviolet visible absorption spectrum and an emission spectrum of the phosphorescent organometallic iridium complex shown in Structural Formula (106).

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail using drawing. However, this invention is not limited to the following description, It is possible to change the form and detail in various ways, without deviating from the meaning and range of this invention. Therefore, this invention is limited to the description content of embodiment shown below and is not interpreted.

(Embodiment 1)

In the present embodiment, a light emitting device that can be applied to a light emitting device based on phosphorescent light emission will be described with reference to FIG. 1 using a phosphorescent organic metal iridium complex as a light emitting layer.

The light emitting element shown in this embodiment includes an EL including a light emitting layer 113 between a pair of electrodes (a first electrode (anode) 101 and a second electrode (cathode) 103) as shown in FIG. The layer 102 is provided, and the EL layer 102 includes a hole (or hole) injection layer 111, a hole (or hole) transport layer 112, an electron transport layer 114, and electron injection in addition to the light emitting layer 113. Layer 115, charge generating layer (E) 116, and the like.

By applying a voltage to the light emitting device, holes injected from the first electrode 101 side and electrons injected from the second electrode 103 side recombine in the light emitting layer 113 to bring the phosphorescent organic metal iridium complex into an excited state. Make. And it emits light when the phosphorescent organometallic iridium complex of an excited state returns to a ground state. Thus, the phosphorescent organometallic iridium complex which is one aspect of the present invention functions as a light emitting material in the light emitting device.

In addition, the hole injection layer 111 of the EL layer 102 is a layer including a material having high hole transportability and an acceptor material, and electrons are extracted from the material having high hole transportability by the acceptor material, thereby causing a hole (hole). Is generated. Therefore, holes are injected from the hole injection layer 111 to the light emitting layer 113 through the hole transport layer 112.

In addition, the charge generating layer (E) 116 is a layer containing a material having high hole transportability and an acceptor material. Since electrons are extracted from a material having high hole transportability by the acceptor material, the extracted electrons are injected from the electron injection layer 115 having electron injection property into the light emitting layer 113 through the electron transport layer 114.

Hereinafter, the specific example in manufacturing the light emitting element shown in this embodiment is demonstrated.

As the first electrode (anode) 101 and the second electrode (cathode) 103, a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like can be used. Specifically, indium tin oxide (ITO), indium tin oxide containing silicon or silicon oxide, indium zinc oxide, indium zinc oxide, indium oxide containing zinc oxide, and gold oxide ( Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), titanium ( In addition to Ti), elements belonging to Group 1 or 2 of the Periodic Table of Elements, that is, alkali metals such as lithium (Li) and cesium (Cs), and alkaline earth metals such as calcium (Ca) and strontium (Sr), magnesium Rare earth metals such as (Mg), alloys containing them (MgAg, AlLi), europium (Eu), ytterbium (Yb), alloys containing them, and other graphenes. In addition, the 1st electrode (anode) 101 and the 2nd electrode (cathode) 103 can be formed, for example by a sputtering method or vapor deposition method (including a vacuum vapor deposition method).

As a material with high hole transportability used for the hole injection layer 111, the hole transport layer 112, and the charge generation layer (E) 116, it is 4,4'-bis [N- (1-naphthyl), for example. ) -N-phenylamino] biphenyl (abbreviated as: NPB or α-NPD) or N, N′-bis (3-methylphenyl) -N, N′-diphenyl- [1,1′-biphenyl] -4 , 4′-diamine (abbreviated: TPD), 4, 4 ′, 4′-tris (carbazol-9-yl) triphenylamine (abbreviated: TCTA), 4, 4 ′, 4′-tris (N , N-diphenylamino) triphenylamine (abbreviated: TDATA), 4, 4 ', 4'-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (abbreviated: MTDATA), 4 And aromatic amine compounds such as 4′-bis [N- (spiro-9,9′-bifluoren-2-yl) -N-phenylamino] biphenyl (abbreviated as: BSPB), and 3- [N- (9 -Phenylcarbazol-3-yl) -N-phenylamino] -9-phenylcarbazole (abbreviated: PCzPCA1), 3, 6-bis [N- (9-phenylcarbazol-3-yl) -N-phenyl Amino] -9-phenylcarbazole (abbreviated: PCzPCA2), 3- [N- (1-naphthyl) -N- (9-phenylcarbazol-3-yl) amino] -9-phenylcarbazole (abbreviated: PCzP CN1) etc. can be mentioned. Other 4,4'-di (N-carbazolyl) biphenyl (abbreviated as: CBP), 1, 3, 5-tris [4- (N-carbazolyl) phenyl] benzene (abbreviated as: TCPB), 9- [ Carbazole derivatives such as 4- (10-phenyl-9-anthracenyl) phenyl] -9H-carbazole (abbreviated as: CzPA) and the like can be used. The materials described herein are mainly materials having a hole mobility of 10 ⁻⁶ cm ² / Vs or more. However, if it is a substance with a higher hole transport property than an electron, you may use other than these.

Furthermore, poly (N-vinylcarbazole) (abbreviation: PVK), poly (4-vinyl triphenylamine) (abbreviation: PVTPA), poly [N- (4-'N '-[4- (4-diphenylamino) ) Phenyl] phenyl-N'-phenylamino｝ phenyl) methacrylamide] (abbreviated as: PTPDMA), poly [N, N'-bis (4-butylphenyl) -N, N'-bis (phenyl) benzidine] ( It is also possible to use a high molecular compound such as poly-TPD).

Examples of the acceptor material used for the hole injection layer 111 and the charge generation layer (E) 116 include transition metal oxides and oxides of metals belonging to Groups 4 to 8 in the Periodic Table of Elements. have. Specifically, molybdenum oxide is particularly preferable.

The light emitting layer 113 contains a phosphorescent organometallic iridium complex as a guest material which becomes a luminescent material, and is a layer formed using a substance with triplet excitation energy larger than this phosphorescent organometallic iridium complex as a host material.

In addition, in the phosphorescent organometallic iridium complex, nitrogen at the 3rd position of pyrimidine having an aryl group at 4th position is coordinated to iridium, and at any one of the 2nd, 5th and 6th positions of pyrimidine has an alkyl group or an aryl group. The aryl group at the 4th position of midine is a phosphorescent organometallic iridium complex having an ortho metallized structure by bonding with iridium, and has a structure represented by the following general formula (G1).

(Wherein Ar represents a substituted or unsubstituted aryl group, and R ¹ to R ³ each independently represent hydrogen, a substituted or unsubstituted C 1-4 alkyl group, or a substituted or unsubstituted C 6-10 aryl group). And at least one of R ¹ to R ³ represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.)

Furthermore, in said phosphorescent organometallic iridium complex, the nitrogen of the 1st position of 1, 3, 5-triazine which has an aryl group in 2nd position coordinates to iridium, and among the 4th and 6th positions of 1, 3, 5-triazine. The aryl group which has a substituent in any one is a phosphorescent organometallic iridium complex which has an ortho metallized structure by couple | bonding with iridium, The thing which has a structure represented by following General formula (G2) can also be used.

(Wherein Ar represents a substituted or unsubstituted aryl group, R ⁴ and R ⁵ each independently represent hydrogen, a substituted or unsubstituted C 1-4 alkyl group, a substituted or unsubstituted C 1-4 alkoxy group) , A substituted or unsubstituted C1-C4 alkylthio group, a halogen group, a substituted or unsubstituted C1-C4 haloalkyl group, or a substituted or unsubstituted C6-C10 aryl group. Provided that at least one of R ⁴ to R ⁵ is a substituted or unsubstituted C 1-4 alkyl group, a substituted or unsubstituted C 1-4 alkoxy group, a substituted or unsubstituted C 1-4 alkylthio group, A halogen group, a substituted or unsubstituted haloalkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.)

Here, the phosphorescent organometallic iridium complex having the structures represented by the general formulas (G1) and (G2), in which the lowest triplet excited state is formed, is preferable since it can efficiently emit phosphorescence. In order to realize such an embodiment, for example, the lowest triplet excitation energy of the structure may be equal to or lower than the lowest triplet excitation energy of the other skeleton (other ligands) constituting the phosphorescent organometallic iridium complex. Other ligands). In this way, the final triplet excited state is finally formed in the structure even if the skeleton (ligator) other than the above structure is formed, so that phosphorescence emission derived from the structure can be obtained. Thus, highly efficient phosphorescence emission can be obtained. For example, a vinyl polymer etc. which have this structure as a side chain are mentioned.

Moreover, as a phosphorescent organometallic iridium complex which has a structure represented by general formula (G1) mentioned above, the phosphorescent organometallic iridium complex represented by the following general formula (G3) is more preferable.

(Wherein Ar represents a substituted or unsubstituted aryl group, and R ¹ to R ³ each independently represent hydrogen, a substituted or unsubstituted C 1-4 alkyl group, or a substituted or unsubstituted C 6-10 aryl group). Provided that at least one of R ¹ to R ³ represents either a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. , L represents a monoanionic ligand.)

Moreover, as a phosphorescent organometallic iridium complex which has a structure represented by general formula (G2) mentioned above, the phosphorescent organometallic iridium complex represented by the following general formula (G4) is more preferable.

(Wherein Ar represents a substituted or unsubstituted aryl group, R ⁴ and R ⁵ each independently represent hydrogen, a substituted or unsubstituted C 1-4 alkyl group, a substituted or unsubstituted C 1-4 alkoxy group) , A substituted or unsubstituted C1-C4 alkylthio group, a halogen group, a substituted or unsubstituted C1-C4 haloalkyl group, or a substituted or unsubstituted C6-C10 aryl group. Provided that at least one of R ⁴ to R ⁵ is a substituted or unsubstituted C 1-4 alkyl group, a substituted or unsubstituted C 1-4 alkoxy group, a substituted or unsubstituted C 1-4 alkylthio group, A halogen group, a substituted or unsubstituted haloalkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and L represents a monoanionic ligand.)

In addition, the monoanionic ligand L in the general formulas (G3) and (G4) described above is a monoanionic bidentate chelate ligand having a betadiketone structure, or a monoanionic bidentate chelate ligand having a carboxyl group, or a phenolic compound. Preferred is either a monoanionic bidentate chelate ligand having a hydroxyl group or a monoanionic bidentate chelate ligand in which both coordination elements are nitrogen. Especially preferably, it is a monoanionic ligand represented by the following structural formulas (L1) to (L7). These ligands are effective because of their high coordination ability and low availability.

(Wherein, R ² 1 to R ⁵⁸ are each independently hydrogen, a substituted or unsubstituted C 1-4 alkyl group, a halogen group, a vinyl group, a substituted or unsubstituted C 1-4 haloalkyl group, substituted or An unsubstituted alkoxy group having 1 to 4 carbon atoms or a substituted or unsubstituted alkylthio group having 1 to 4. In addition, each of A ¹ to A ⁴ independently represents sp ² hybrid carbon bonded to nitrogen and hydrogen, Or sp ² hybrid carbon bonded to substituent R, and substituent R represents an alkyl group having 1 to 4 carbon atoms, a halogen group, a haloalkyl group having 1 to 4 carbon atoms, or a phenyl group.)

Moreover, as a phosphorescent organometallic iridium complex which has a structure represented by general formula (G1) mentioned above, the phosphorescent organometallic iridium complex represented by the following general formula (G5) is more preferable.

(Wherein Ar represents a substituted or unsubstituted aryl group, and R ¹ to R ³ each independently represent hydrogen, a substituted or unsubstituted C 1-4 alkyl group, or a substituted or unsubstituted C 6-10 aryl group). And at least one of R ¹ to R ³ represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.)

Moreover, as a phosphorescent organometallic iridium complex which has a structure represented by general formula (G2) mentioned above, the phosphorescent organometallic iridium complex represented by the following general formula (G6) is more preferable.

(Wherein Ar represents a substituted or unsubstituted aryl group, R ⁴ and R ⁵ each independently represent hydrogen, a substituted or unsubstituted C 1-4 alkyl group, a substituted or unsubstituted C 1-4 alkoxy group) , A substituted or unsubstituted C1-C4 alkylthio group, a halogen group, a substituted or unsubstituted C1-C4 haloalkyl group, or a substituted or unsubstituted C6-C10 aryl group. Provided that at least one of R ⁴ to R ⁵ is a substituted or unsubstituted C 1-4 alkyl group, a substituted or unsubstituted C 1-4 alkoxy group, a substituted or unsubstituted C 1-4 alkylthio group, A halogen group, a substituted or unsubstituted haloalkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.)

Moreover, as a phosphorescent organometallic iridium complex which has a structure represented by general formula (G1)-(G6) mentioned above, specifically, the phosphorescent organometallic iridium complex represented by following structural formula (100)-(106) is more preferable.

In addition, as a substance (namely, a host material) used for making the said phosphorescent organometallic iridium complex into a dispersed state, 4-phenyl-4 '-(9-phenyl-9H-carbazol-3-yl), for example. Triphenylamine (abbreviated: PCBA1BP), 3- [N- (1-naphthyl) -N- (9-phenylcarbazol-3-yl) amino] -9-phenylcarbazole (abbreviated: PCzPCN1), 2, In addition to compounds having an arylamine skeleton such as 3-bis (4-diphenylaminophenyl) quinoxaline (abbreviated as: TPAQn), NPB, CBP, 4, 4 ', 4'-tris (carbazol-9-yl ) Carbazole derivatives such as triphenylamine (abbreviation: TCTA), 2- [3- (dibenzothiophen-4-yl) phenyl] dibenzo [f, h] quinoxaline (abbreviation: 2mDBTPDBq-II), 2- [3 ′-(dibenzothiophen-4-yl) biphenyl-3-yl] dibenzo [f, h] quinoxaline (abbreviated: 2mDBTBPDBq-II), 2- [4- (3, 6- Nitrogen-containing heteroaromatic compounds such as diphenyl-9H-carbazol-9-yl) phenyl] dibenzo [f, h] quinoxaline (abbreviated: 2CzPDBq-III), or bis [2- (2-hydroxyphenyl) Pyridinato] zinc (abbreviated: Znpp ₂ ), bis [2- (2- Hydroxyphenyl) benzooxazolato] zinc (abbreviated: Zn (BOX) ₂ ), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (abbreviated: BAl _q ), tris ( 8-quinolinolato) aluminum (abbreviation: Alq ₃₎ is preferably a metal complex or the like. It is also possible to use a polymer compound such as PVK.

In the case of the light emitting layer 113, the phosphorescent organometallic iridium complex (guest material) and the host material described above are formed to provide phosphorescent light emission having high luminous efficiency from the light emitting layer 113.

The electron transport layer 114 is a layer containing a material having high electron transport property. The electron transport layer 114 includes Alq ₃ , tris (4-methyl-8-quinolinolato) aluminum (abbreviated as: Almq ₃ ), bis (10-hydroxybenzo [h] quinolinato) beryllium (abbreviated as: BeBq). ₂ ), metal complexes such as BAlq, Zn (BOX) ₂ and bis [2- (2-hydroxyphenyl) benzothiazolato] zinc (abbreviated as: Zn (BTZ) ₂ ) can be used. In addition, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1, 3, 4-oxadiazole (abbreviated as: PBD), 1, 3-bis [5- (p-tert -Butylphenyl) -1,3,4-oxadiazol-2-yl] benzene (abbreviated: OXD-7), 3- (4-tert-butylphenyl) -4-phenyl-5- (4-biphenyl Reyl) -1, 2, 4-triazole (abbreviation: TAZ), 3- (4-tert-butylphenyl) -4- (4-ethylphenyl) -5- (4-biphenylyl) -1, 2 , 4-triazole (abbreviation: p-EtTAZ), vasophenanthroline (abbreviation: Bphen), vasocuproin (abbreviation: BCP), 4, 4'-bis (5-methylbenzooxazol-2-yl A heteroaromatic compound, such as steelbene (abbreviation: BzOs), can also be used. Further, poly (2, 5-pyridindiyl) (abbreviated as: PPy), poly [(9, 9-dihexylfluorene-2, 7-diyl) -co- (pyridine-3, 5-diyl)] (abbreviated) : PF-Py), poly [(9,9-dioctylfluorene-2, 7-diyl) -co- (2,2′-bipyridine-6,6′-diyl)] (abbreviated as: PF-BPy It is also possible to use a polymer compound such as). The materials described herein are mainly materials having an electron mobility of 10 ⁻⁶ cm ² / Vs or more. In addition, the substance other than the above can also be used as an electron carrying layer as long as it is a substance with higher electron transport property than a hole.

The electron transport layer 114 may be formed by stacking not only a single layer but also two or more layers made of the above materials.

The electron injection layer 115 is a layer containing a substance having a high electron injecting property. The electron injection layer 115 may be an alkali metal, an alkaline earth metal, or a compound thereof, such as lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF ₂ ), lithium oxide (LiOx), or the like. It is also possible to use rare earth metal compounds such as erbium fluoride (ErF ₃ ). In addition, the materials constituting the above-described electron transport layer 114 may be used.

Alternatively, a composite material obtained by mixing an organic compound and an electron donor (donor) may be used for the electron injection layer 115. Such a composite material is excellent in electron injection property and electron transport property because electrons are generated in an organic compound by an electron donor. In this case, it is preferable that it is a material excellent in the transport of the generated electron as an organic compound, Specifically, the substance (metal complex, heteroaromatic compound, etc.) which comprises the above-mentioned electron transport layer 114 can be used, for example. . As an electron donor, the substance which shows an electron donating can be used with respect to an organic compound. Specifically, alkali metals, alkaline earth metals, and rare earth metals are preferable, and lithium, cesium, magnesium, calcium, erbium, ytterbium, and the like can be given. Moreover, alkali metal oxide and alkaline earth metal oxide are preferable, and lithium oxide, calcium oxide, barium oxide, etc. are mentioned. It is also possible to use Lewis bases such as magnesium oxide. Moreover, organic compounds, such as tetrathiaple valent (abbreviation: TTF), can also be used.

In addition, the hole injection layer 111, the hole transport layer 112, the light emitting layer 113, the electron transport layer 114, the electron injection layer 115, and the charge generating layer (E) 116 described above are respectively deposited (vacuum deposition method). It can be formed by a method such as), an inkjet method, a coating method and the like.

The above-described light emitting element emits light when current flows due to a potential difference generated between the first electrode 101 and the second electrode 103 so that holes and electrons recombine in the EL layer 102. The light emission is extracted to the outside via any one or both of the first electrode 101 and the second electrode 103. Therefore, either or both of the first electrode 101 and the second electrode 103 becomes an electrode having light transparency.

The light emitting device described above can obtain phosphorescent light emission based on the phosphorescent organometallic iridium complex, and thus can achieve a light emitting device having high efficiency as compared with the light emitting device using the fluorescent compound.

In addition, although the light emitting element shown in this embodiment is an example of the structure of a light emitting element, the light emitting element of another structure can also be applied to the light emitting device which is one aspect of this invention. The light emitting device including the light emitting element may include a microcavity structure including a passive matrix light emitting device or an active matrix light emitting device, and a light emitting device having a structure different from that described above in another embodiment. A light emitting device and the like can be manufactured and all of them are included in the present invention.

In the case of the active matrix light emitting device, the structure of the TFT is not particularly limited. For example, a staggered or reverse staggered TFT can be suitably used. Further, the driving circuit formed on the TFT substrate may also be composed of N-type and P-type TFTs, or may be composed of only one of N-type TFTs or P-type TFTs. Further, the crystallinity of the semiconductor film used for the TFT is not particularly limited. For example, an amorphous semiconductor film, a crystalline semiconductor film, another oxide semiconductor film, or the like can be used.

In addition, the structure shown in this embodiment can be used suitably combining with the structure shown in other embodiment.

(Embodiment 2)

In this embodiment, in addition to the phosphorescent organometallic iridium complex as one embodiment of the present invention, a light emitting device using two or more different organic compounds for the light emitting layer will be described.

As shown in FIG. 2, the light emitting element shown in this embodiment has a structure having an EL layer 203 between a pair of electrodes (anode 201 and cathode 202). In addition, the EL layer 203 may have at least the light emitting layer 204, and may further include a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a charge generating layer E, and the like. In addition, the material shown in Embodiment 1 can be used for a hole injection layer, a hole transport layer, an electron carrying layer, an electron injection layer, and a charge generating layer (E).

The light emitting layer 204 shown in this embodiment contains the phosphorescent compound 205, the 1st organic compound 206, and the 2nd organic compound 207 using the phosphorescent organometallic iridium complex shown in Embodiment 1. As shown in FIG. In addition, the phosphorescent compound 205 is a guest material of the light emitting layer 204. In addition, the ratio of the 1st organic compound 206 and the 2nd organic compound 207 contained in the light emitting layer 204 is made into the host material of the light emitting layer 204.

In the light emitting layer 204, crystallization of the light emitting layer can be suppressed by dispersing the guest material in the host material. In addition, the concentration quenching due to the high concentration of the guest material can be suppressed to increase the luminous efficiency of the light emitting device.

In addition, the triplet excitation energy level (T ₁ level) of each of the first organic compound 206 and the second organic compound 207 is preferably higher than the T ₁ level of the phosphorescent compound 205. When the T ₁ level of the first organic compound 206 (or the second organic compound 207) is lower than the T ₁ level of the phosphorescent compound 205, triplet excitation of the phosphorescent compound 205 that contributes to light emission This is because the energy is quenched (quenched) by the first organic compound 206 (or the second organic compound 207), resulting in a decrease in luminous efficiency.

Here, in order to increase the energy transfer efficiency from the host material to the guest material, in consideration of the Muxter mechanism (dipole-dipole interaction) and the Dexter mechanism (electron exchange interaction), which are known as intermolecular energy transfer mechanisms, The emission spectrum of the host material (fluorescence spectrum when discussing the energy transfer from the singlet excited state, the phosphorescence spectrum when discussing the energy transfer from the triplet excited state) and the absorption spectrum of the guest material (more specifically, It is preferable that the overlap with the spectrum in the absorption band on the longest wavelength (low energy) side becomes larger. However, it is usually difficult to overlap the fluorescence spectrum of the host material with the absorption spectrum in the absorption band on the longest wavelength (low energy) side of the guest material. Because then the phosphorescence spectrum of the host material is located on the longer wavelength (low energy) side of the fluorescence spectrum, so T ₁ of the host material This is because the level is lower than the T ₁ level of the phosphorescent compound, which causes the above-mentioned quenching problem. On the other hand, when designing the T ₁ level of the host material in order to avoid quantization justification problem to above the T ₁ level of the phosphorescent compound, since this time to shift the fluorescence spectrum of the host material, the short wavelength side (high energy) that fluorescence spectra The absorption spectrum at the absorption band on the longest wavelength (low energy) side of the guest material does not overlap. Therefore, it is usually difficult to maximize the energy transfer from the singlet excited state of the host material by overlapping the fluorescence spectrum of the host material with the absorption spectrum in the absorption band on the longest wavelength (low energy) side of the guest material.

Therefore, in this embodiment, it is preferable that a 1st organic compound and a 2nd organic compound are a combination which forms an exciplex (it is also called an exciplex). In this case, the first organic compound 206 and the second organic compound 207 form an exciplex at the recombination of carriers (electrons and holes) of the light emitting layer 204. Thereby, in the light emitting layer 204, the fluorescence spectrum of the 1st organic compound 206 and the fluorescence spectrum of the 2nd organic compound 207 are converted into the emission spectrum of the exciplex which is located in the longer wavelength side. When the first organic compound and the second organic compound are selected so that the overlap between the emission spectrum of the exciplex and the absorption spectrum of the guest material is increased, the energy transfer from the singlet excited state can be maximized. In the triplet excited state, energy transfer from the exciplex rather than the host material is considered to occur.

As the phosphorescent compound 205, the phosphorescent organometallic iridium complex shown in Embodiment 1 is used. As the first organic compound 206 and the second organic compound 207, a combination which causes an exciplex can be used. A compound (electron trapping compound) that is easy to accept electrons and a compound (hole trap) that is easy to accept holes are used. Sex compound).

As a compound which is easy to accept an electron, (pi) electron deficient type | mold aromatic compound, such as a nitrogen-containing heteroaromatic compound, is preferable, for example, 2- [3- (dibenzothiophen-4-yl) phenyl] dibenzo [f , h] quinoxaline (abbreviated: 2mDBTPDBq-II), 2- [3 ′-(dibenzothiophen-4-yl) biphenyl-3-yl] dibenzo [f, h] quinoxaline (abbreviated: 2mDBTBPDBq- II), 2- [4- (3, 6-diphenyl-9H-carbazol-9-yl) phenyl] dibenzo [f, h] quinoxaline (abbreviated: 2CzPDBq-III), 7- [3- ( Dibenzothiophen-4-yl) phenyl] dibenzo [f, h] quinoxaline (abbreviated: 7mDBTPDBq-II), and 6- [3- (dibenzothiophen-4-yl) phenyl] dibenzo [f and quinoxaline or dibenzoquinoxaline derivatives such as h] quinoxaline (abbreviated name: 6mDBTPDBq-II).

As a compound which is easy to accommodate a hole, (pi) electron excess type hetero aromatic compound (for example, a carbazole derivative or an indole derivative) and an aromatic amine compound are preferable, For example, 4-phenyl-4 '-(9-phenyl-9H- Carbazol-3-yl) triphenylamine (abbreviated as: PCBA1BP), 4,4'-di (1-naphthyl) -4 '-(9-phenyl-9H-carbazol-3-yl) triphenylamine (Abbreviated name: PCBNBB), 3- [N- (1-naphthyl) -N- (9-phenylcarbazol-3-yl) amino] -9-phenylcarbazole (abbreviated: PCzPCN1), 4, 4 ', 4′-tris [N- (1-naphthyl) -N-phenylamino] triphenylamine (abbreviated as: 1′-TNATA), 2, 7-bis [N- (4-diphenylaminophenyl) -N -Phenylamino] -spiro-9, 9'-bifluorene (abbreviated: DPA2SF), N, N'-bis (9-phenylcarbazol-3-yl) -N, N'-diphenylbenzene-1, 3-diamine (abbreviated: PCA2B), N- (9, 9-dimethyl-2-N ', N'-diphenylamino-9H-fluoren-7-yl) diphenylamine (abbreviated: DPNF), N, N ', N'-triphenyl-N, N', N'-tris (9-phenylcarbazol-3-yl) benzene-1, 3, 5-triamine ( Ching: PCA3B), 2- [N- (9-phenylcarbazol-3-yl) -N-phenylamino] spiro-9, 9′-bifluorene (abbreviated: PCASF), 2- [N- (4 -Diphenylaminophenyl) -N-phenylamino] spiro-9,9'-bifluorene (abbreviated as: DPASF), N, N'-bis [4- (carbazol-9-yl) phenyl] -N, N'-diphenyl-9, 9-dimethylfluorene-2, 7-diamine (abbreviated: YGA2F), 4, 4'-bis [N- (3-methylphenyl) -N-phenylamino] biphenyl (abbreviated: TPD), 4,4′-bis [N- (4-diphenylaminophenyl) -N-phenylamino] biphenyl (abbreviated as: DPAB), N- (9, 9-dimethyl-9H-fluorene-2- Yl) -N- ｛9, 9-dimethyl-2- [N＇-phenyl-N ＇-(9, 9-dimethyl-9H-fluoren-2-yl) amino] -9H-fluoren-7-yl ｝ Phenylamine (abbreviated as: DFLADFL), 3- [N- (9-phenylcarbazol-3-yl) -N-phenylamino] -9-phenylcarbazole (abbreviated as: PCzPCA1), 3- [N- (4 -Diphenylaminophenyl) -N-phenylamino] -9-phenylcarbazole (abbreviated as: PCzDPA1), 3, 6-bis [N- (4-diphenylaminophenyl) -N-phenylamino] -9-phenyl Carbazole (abbreviated name: PCzDPA2), 4, 4′-bis (N-′4- [N ′-(3-methylphenyl) -N′-peh Amino] phenyl｝ -N-phenylamino) biphenyl (abbreviated as: DNTPD), 3, 6-bis [N- (4-diphenylaminophenyl) -N- (1-naphthyl) amino] -9-phenylcarba Sol (abbreviated: PCzTPN2), 3, 6-bis [N- (9-phenylcarbazol-3-yl) -N-phenylamino] -9-phenylcarbazole (abbreviated: PCzPCA2).

The first organic compound 206 and the second organic compound 207 described above are not limited thereto, and a combination capable of forming an exciplex, wherein the emission spectrum of the exciplex is overlapped with the absorption spectrum of the phosphorescent compound 205 and is excited. The peak of the emission spectrum of the complex may be longer than the peak of the absorption spectrum of the phosphorescent compound 205.

In addition, when the first organic compound 206 and the second organic compound 207 are composed of a compound which is easy to accept electrons and a compound that is capable of accepting holes, the carrier balance can be controlled by the mixing ratio. Specifically, the range of 1st organic compound: 2nd organic compound = 1: 9-9: 1 is preferable.

The light emitting element shown in the present embodiment can increase the energy transfer efficiency by the energy transfer using the superposition of the emission spectrum of the exciplex and the absorption spectrum of the phosphorescent compound, thereby realizing a light emitting element having high external quantum efficiency.

In addition to the phosphorescent compound 205 (guest material) as another structure included in the present invention, the light emitting layer 204 is formed by using two kinds of organic compounds, the hole trapping host molecule and the electron trapping host molecule. The light emitting layer 204 may be formed to introduce a hole and an electron into a guest molecule present in the host molecule to obtain a guest molecule in an excited state (ie, Guest Coupled with Complementary Hosts (GCCH)).

At this time, as the host molecule of a hole trapping property and the host molecule of an electron trapping property, the compound which is easy to accept the above-mentioned hole, and the compound which is easy to accept an electron can be used, respectively.

In addition, although the light emitting element shown in this embodiment is an example of the structure of a light emitting element, the light emitting element of another aspect can also be applied to the light emitting device which is one aspect of this invention. The light emitting device including the light emitting element may include a microcavity structure including a light emitting device having a structure different from that described in other embodiments, in addition to the passive matrix light emitting device or the active matrix light emitting device. Light emitting devices and the like can all be included in the present invention.

In the case of the active matrix light emitting device, the structure of the TFT is not particularly limited. For example, a staggered or reverse staggered TFT can be suitably used. Further, the driving circuit formed on the TFT substrate may also be composed of N-type and P-type TFTs, or may be made of only one of N-type TFTs or P-type TFTs. Furthermore, the crystallinity of the semiconductor film used for TFT is not specifically limited, either. For example, an amorphous semiconductor film, a crystalline semiconductor film, an oxide semiconductor film, or the like can be used.

In addition, the structure shown in this embodiment shall be used combining suitably with the structure shown in other embodiment.

(Embodiment 3)

In this embodiment, as one aspect of the present invention, a light emitting device (hereinafter referred to as a tandem light emitting device) having a structure having a plurality of EL layers with a charge generating layer therebetween will be described.

In the light emitting element shown in this embodiment, as shown in Fig. 3A, a plurality of EL layers (first EL layer 302) are provided between a pair of electrodes (the first electrode 301 and the second electrode 304). (1)) and a tandem light emitting element having a second EL layer 302 (2).

In this embodiment, the 1st electrode 301 is an electrode which functions as an anode, and the 2nd electrode 304 is an electrode which functions as a cathode. In addition, the 1st electrode 301 and the 2nd electrode 304 can use the structure similar to 1st Embodiment. The plurality of EL layers (first EL layer 302 (1) and second EL layer 302 (2)) may have the same configuration as the EL layer shown in Embodiment 1 or Embodiment 2, but either May be the same configuration. That is, the first EL layer 302 (1) and the second EL layer 302 (2) may have the same configuration or different configurations, and the configuration thereof may be the same as the first embodiment or the second embodiment. .

In addition, a charge generation layer (I) 305 is provided between the plurality of EL layers (first EL layer 302 (1) and second EL layer 302 (2)). The charge generation layer (I) 305 injects electrons into one EL layer and holes in another EL layer when a voltage is applied to the first electrode 301 and the second electrode 304. Has In the present embodiment, when a voltage is applied to the first electrode 301 so as to have a higher potential than the second electrode 304, electrons are generated from the charge generation layer (I) 305 to the first EL layer 302 (1). Is injected and holes are injected into the second EL layer 302 (2).

In addition, it is preferable that the charge generating layer (I) 305 has light transmittance with respect to visible light in terms of light extraction efficiency (specifically, the transmittance of visible light with respect to the charge generating layer (I) 305 is 40% or more). In addition, the charge generation layer (I) 305 functions even if the conductivity is lower than that of the first electrode 301 or the second electrode 304.

The charge generating layer (I) 305 may have a structure in which an electron acceptor (acceptor) is added to an organic compound having high hole transportability, or a structure in which an electron donor (donor) is added to an organic compound having high electron transportability. In addition, the two structures may be laminated.

When the electron acceptor is added to the organic compound having high hole transportability, examples of the organic compound having high hole transportability include, for example, NPB, TPD, TDATA, MTDATA, 4, and 4′-bis [N- (spiro-9, 9′-ratios). Aromatic amine compounds such as fluoren-2-yl) -N-phenylamino] biphenyl (abbreviated as: BSPB) and the like can be used. The materials described herein are mainly materials having a hole mobility of 10 ⁻⁶ cm ² / Vs or more. However, as long as it is an organic compound having higher transportability of holes than electrons, substances other than those described above may be used.

Examples of the electron acceptor include 7, 7, 8, 8-tetracyano-2, 3, 5, and 6-tetrafluoroquinodimethane (abbreviated as: F ₄ -TCNQ), chloranyl and the like. In addition, transition metal oxides may be mentioned. Moreover, the oxide of the metal which belongs to the 4th group-8th group in an element periodic table is mentioned. Specifically, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, and rhenium oxide are preferable because they have high electron acceptability. Among them, molybdenum oxide is particularly preferable because it is stable in the air, has low hygroscopicity and is easy to handle.

On the other hand, in the case of adding an electron donor to an organic compound having high electron transportability, for example, a metal complex having a quinoline skeleton or a benzoquinoline skeleton, such as Alq, Almq ₃ , BeBq ₂ , or BAlq, may be used as the organic compound having high electron transportability. Can be. In addition, a metal complex having an oxazole-based or thiazole-based ligand such as Zn (BOX) ₂ or Zn (BTZ) ₂ can also be used. Furthermore, in addition to metal complexes, PBD, OXD-7, TAZ, Bphen, BCP and the like can also be used. The materials described herein are mainly materials having an electron mobility of 10 ⁻⁶ cm ² / Vs or more. In addition, if it is an organic compound with higher electron transport property than a hole, substances other than the above can also be used.

As the electron donor, an alkali metal, an alkaline earth metal, a rare earth metal, or a metal belonging to Groups 2 and 13 in the Periodic Table of the Elements, oxides and carbonates thereof can be used. Specifically, lithium (Li), cesium (Cs), magnesium (Mg), calcium (Ca), ytterbium (Yb), indium (In), lithium oxide, cesium carbonate, or the like is preferably used. It is also possible to use organic compounds such as tetrathianaphthacene as electron donors.

In addition, by forming the charge generating layer (I) 305 using the above-described materials, it is possible to suppress the increase in the driving voltage when the EL layers are laminated.

In the present embodiment, a light emitting device having two EL layers has been described, but the same applies to a light emitting device in which n layers (where n is three or more) are laminated in the same manner as shown in Fig. 3B. It is possible to. In the case of having a plurality of EL layers between a pair of electrodes as in the light emitting device according to the present embodiment, a high luminance region is maintained with a low current density by disposing the charge generating layer I between the EL layers and the EL layers. Can emit light. Since the current density can be kept low, a long life element can be realized. In addition, when illumination is used as an application example, the voltage drop due to the resistance of the electrode material can be reduced, so that uniform light emission at a large area is possible. In addition, it is possible to drive a low voltage can realize a light emitting device with low power consumption.

In addition, by changing the light emission color of each EL layer, light emission of a desired color can be obtained as a whole of the light emitting element. For example, in a light emitting device having two EL layers, a light emitting device emitting white light as a whole can be obtained by making the light emission color of the first EL layer and the light emission color of the second EL layer a complementary color. In addition, complementary color refers to the relationship between the colors which become achromatic when mixed. In other words, white light emission can be obtained by mixing light obtained from a material that emits a color having a complementary color relationship.

The same applies to the light emitting device having three EL layers. For example, when the light emitting color of the first EL layer is red, the light emitting color of the second EL layer is green, and the light emitting color of the third EL layer is blue, White light emission can be obtained.

In addition, the structure shown in this embodiment can be used suitably combining with the structure shown in other embodiment.

(Fourth Embodiment)

In this embodiment, a light emitting device using a phosphorescent organometallic iridium complex as a light emitting device based on phosphorescent light emission, which is one embodiment of the present invention, will be described.

The light emitting device shown in this embodiment has a micro-optical resonator (micro cavity) structure using the resonance effect of light between a pair of electrodes, and as shown in FIG. 4, a pair of electrodes (reflective electrode 401 and There are a plurality of light emitting elements having a structure having at least an EL layer 405 between the semi-transmissive and semi-reflective electrodes 402. In addition, the EL layer 405 has at least the light emitting layer 404 serving as a light emitting region, and may also include a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a charge generating layer E, and the like. In addition, the light emitting layer 404 contains a phosphorescent organometallic iridium complex which is one embodiment of the present invention.

In this embodiment, as shown in Fig. 4, light emitting devices having different structures (first light emitting device (R) 410R, second light emitting device (G) 410G, and third light emitting device (B) 410B) A light emitting device including the above will be described.

The first light emitting device (R) 410R includes a first transparent conductive layer 403a, a first light emitting layer (B) 404B, a second light emitting layer (G) 404G, and a third layer on the reflective electrode 401. The EL layer 405 including a part of the light emitting layer (R) 404R and the semi-transmissive semi-reflective electrode 402 are sequentially stacked. In the second light emitting element (G) 410G, the second transparent conductive layer 403b, the EL layer 405, and the semi-transmissive semi-reflective electrode 402 are sequentially stacked on the reflective electrode 401. Has a structure. The third light emitting element (B) 410B has a structure in which an EL layer 405 and a semi-transmissive semi-reflective electrode 402 are sequentially stacked on the reflective electrode 401.

In addition, in the light emitting device (the first light emitting device (R) 410R, the second light emitting device (G) 410G, and the third light emitting device (B) 410B), the reflective electrode 401 and the EL layer 405 ), The semi-transmissive semi-reflective electrode 402 is common. In addition, the first light emitting layer (B) 404B emits light λ _B having a peak in a wavelength region of 420 nm or more and 480 nm or less, and the second light emitting layer (G) 404G emits light in a wavelength region of 500 nm or more and 550 nm or less. Light (λ _G ) having a peak is emitted, and light (λ _R ) having a peak is emitted in a wavelength region of 600 nm or more and 760 nm or less in the third light emitting layer (R) 404R. As a result, the first light emitting layer (B) 404B in all the light emitting devices (the first light emitting device (R) 410R, the second light emitting device (G) 410G, and the third light emitting device (B) 410B). In addition, the light emission from the second light emitting layer (G) 404G and the third light emitting layer (R) 404R may be superimposed and combined, that is, to emit a broad light emission spectrum over the visible light region. By the above, it is assumed that the length of the wavelength is such that λ _B <λ _G <λ _R.

Each light emitting element shown in this embodiment has a structure in which an EL layer 405 is provided between the reflective electrode 401 and the semi-transmissive semi-reflective electrode 402, respectively, and each of the light emitting layers included in the EL layer 405. The light emitted from all directions from the side is resonated by the reflective electrode 401 and the semi-transmissive semi-reflective electrode 402 which function as a micro light resonator (micro cavity). In addition, the reflective electrode 401 is formed from a conductive material having reflectivity, and the reflectivity of the visible light 40% to 100%, preferably 70% ~ 100% of that membrane, as well as the resistivity is 1 × 10 ^{- 2} Ωcm Assume that the film is as follows. In addition, the semi-transmissive semi-reflective electrode 402 is formed of a reflective conductive material and a light-transmissive conductive material, and the reflectance of visible light to the film is 20% to 80%, preferably 40% to 70%. In addition, it is assumed that the film has a resistivity of 1 × 10 ⁻² Ωcm or less.

In the present embodiment, each of the light emitting devices includes a transparent conductive layer (first transparent conductive layer 403a and a second layer) provided in each of the first light emitting device (R) 410R and the second light emitting device (G) 410G. By changing the thickness of the transparent conductive layer 403b, the optical distance between the reflective electrode 401 and the semi-transmissive semi-reflective electrode 402 is changed for each light emitting element. That is, the broad light emission spectrum emitted from each light emitting layer of each light emitting element strengthens the light of the resonant wavelength between the reflective electrode 401 and the semi-transmissive semi-reflective electrode 402 and generates light of the wavelength that does not resonate. Since it can be attenuated, light of different wavelengths can be extracted by changing the optical distance between the reflective electrode 401 and the semi-transmissive semi-reflective electrode 402 for each element.

In addition, in the first light emitting device (R) 410R, the total thickness from the reflective electrode 401 to the semi-transmissive semi-reflective electrode 402 is mλ _R / 2 (where m is a natural number) and the second light emitting device (G). In 410G, the total thickness from the reflective electrode 401 to the semi-transmissive semi-reflective electrode 402 is mλ _G / 2 (where m is a natural number), and in the third light emitting device (B) 410B, the reflective electrode 401 is used. ) To the semi-transmissive semi-reflective electrode 402 is mλ _B / 2 (where m is a natural number).

As a result, the light λ _R emitted from the third light emitting layer R 404R mainly included in the EL layer 405 is extracted from the first light emitting device _R 410R, and the second light emitting device G is extracted. The light λ _G emitted from the second light emitting layer (G) 404G included in the EL layer 405 is mainly extracted from the 410G, and the EL layer is mainly derived from the third light emitting device (B) 410B. Light λ _B emitted from the first light emitting layer (B) 404B included in 405 is extracted. In addition, the light extracted from each light emitting element is emitted from the transflective semi-reflective electrode 402 side, respectively.

Further, in the above configuration, the total thickness from the reflective electrode 401 to the semi-transmissive semi-reflective electrode 402 is strictly the total thickness from the reflective region of the reflective electrode 401 to the reflective region of the semi-transmissive semi-reflective electrode 402. It can be called thickness. However, since it is difficult to precisely determine the position of the reflective region of the reflective electrode 401 or the semi-transmissive semi-reflective electrode 402, the arbitrary positions of the reflective electrode 401 and the semi-transmissive semi-reflective electrode 402 are reflected. By setting it as an area, it is assumed that the above-described effects can be sufficiently obtained.

Subsequently, in the first light emitting device (R) 410R, an optical distance from the reflective electrode 401 to the third light emitting layer (R) 404R is obtained by a desired film thickness ((2m ＇+ 1) λ _R / 4 (where m Can be amplified by the third light emitting layer (R) 404R. Among the light emitted from the third light emitting layer (R) 404R, the light reflected by the reflective electrode 401 (first reflected light) is directly transmitted from the third light emitting layer (R) 404R to the semi-transmissive semi-reflective electrode 402. Interfering with incident light (first incident light), the optical distance from the reflective electrode 401 to the third light emitting layer (R) 404R is a desired value ((2 m ＇+ 1) λ _R / 4 (where m 마련 is a natural number), and the light emission from the third light emitting layer (R) 404R can be amplified by adjusting the phase of the first reflected light and the first incident light.

In addition, the optical distance between the reflective electrode 401 and the third light emitting layer (R) 404R is strictly referred to as the optical distance between the reflective area of the reflective electrode 401 and the light emitting area of the third light emitting layer (R) 404R. Can be. However, since it is difficult to strictly determine the position of the reflective region of the reflective electrode 401 or the light emitting region of the third light emitting layer (R) 404R, any position of the reflective electrode 401 may be selected from the reflective region and the third light emitting layer ( It is assumed that the above-described effects can be sufficiently obtained by setting any position of R) 404R as the light emitting region.

Next, in the second light emitting device (G) 410G, an optical distance from the reflective electrode 401 to the second light emitting layer (G) 404G is obtained by a desired film thickness ((2 m (+1) λ _G / 4 (where, m ＇＇ is a natural number), and the light emission from the second light emitting layer (G) 404G can be amplified. Light emitted from the second light emitting layer (G) 404G and reflected back by the reflective electrode 401 (second reflected light) is directly transmitted from the second light emitting layer (G) 404G to the semi-transmissive semi-reflective electrode 402. Interfering with the incident light (second incident light), the optical distance from the reflective electrode 401 to the second light emitting layer (G) 404G is a desired value ((2m ＇＇ + 1) λ _G / 4 (where m 마련 is a natural number) so that the light emitted from the second light emitting layer (G) 404G can be amplified by adjusting the phase of the second reflected light and the second incident light.

In addition, the optical distance between the reflective electrode 401 and the second light emitting layer (G) 404G is strictly referred to as the optical distance between the reflective area of the reflective electrode 401 and the light emitting area of the second light emitting layer (G) 404G. Can be. However, since it is difficult to strictly determine the position of the reflective region of the reflective electrode 401 or the light emitting region of the second light emitting layer (G) 404G, any position of the reflective electrode 401 may be changed to the reflective region and the second light emitting layer ( It is assumed that the above-described effects can be sufficiently obtained by setting the arbitrary position of G) 404G as the light emitting region.

Next, the optical distance from the reflective electrode 401 to the first light emitting layer (B) 404B in the third light emitting device (B) 410B is a desired film thickness ((2m ＇＇ ＇+ 1) λ _B / 4 (where, m ＇＇ ＇is a natural number), and the light emission from the first light emitting layer (B) 404B can be amplified. Light emitted from the first light emitting layer (B) 404B and reflected back by the reflective electrode 401 (third reflected light) is directly transmitted from the first light emitting layer (B) 404B to the semi-transmissive semi-reflective electrode 402. Interfering with the incident light (third incident light), the optical distance from the reflective electrode 401 to the first light emitting layer (B) 404B is a desired value ((2m ＇＇ ＇+ 1) λ _B / 4 (where, m ＇＇ ＇is a natural number), and the light emission from the first light emitting layer (B) 404B can be amplified by adjusting the phase of the third reflected light and the third incident light.

In addition, in the third light emitting device, the optical distance between the reflective electrode 401 and the first light emitting layer (B) 404B is strictly the reflective area of the reflective electrode 401 and the light emitting area of the first light emitting layer (B) 404B. It can be said to be the optical distance between and. However, since it is difficult to strictly determine the position of the reflective region of the reflective electrode 401 or the light emitting region of the first light emitting layer (B) 404B, any position of the reflective electrode 401 may be selected from the reflective region and the first light emitting layer ( It is assumed that the above-described effects can be sufficiently obtained by setting any position of B) 404B as the light emitting region.

In addition, although all the light emitting elements in the above structure have a structure in which a plurality of light emitting layers are provided on the EL layer, the present invention is not limited thereto, and is combined with the configuration of the tandem type light emitting element described in Embodiment 3 to provide a single light emitting element. A plurality of EL layers may be provided with the charge generating layer interposed therebetween, and a single or a plurality of light emitting layers may be formed in each EL layer.

The light emitting device shown in this embodiment has a micro cavity structure, and even light having different wavelengths can be extracted for each light emitting element even if they have the same EL layer, and there is no need to apply RGB separately. Therefore, it is advantageous in realizing full colorization because it is easy to realize high resolution. In addition, since the light emission intensity in the front direction of the specific wavelength can be strengthened, the power consumption can be reduced. This configuration is particularly useful when applied to a color display (image display device) using pixels of three or more colors, but can also be used for applications such as lighting.

(Embodiment 5)

In the present embodiment, a light emitting device having a light emitting element using a phosphorescent organometallic iridium complex as the light emitting layer as a light emitting device based on phosphorescent light emission, which is an aspect of the present invention, will be described.

Further, the light emitting device based on phosphorescent light emission, which is an aspect of the present invention, may be a passive matrix light emitting device or an active matrix light emitting device. In addition, it is possible to apply the light emitting element described in another embodiment to the light emitting device shown in this embodiment.

In the present embodiment, an active matrix light emitting device as a light emitting device based on phosphorescence, which is an aspect of the present invention, will be described with reference to FIG.

5A is a top view of the light emitting device, and FIG. 5B is a cross-sectional view taken along the line A-A 'of FIG. 5A. In the active matrix light emitting device according to the present embodiment, the pixel portion 502 provided on the element substrate 501, the driving circuit portion (source line driving circuit) 503, and the driving circuit portion (gate line driving circuit) 504 Has The pixel portion 502, the driving circuit portion 503, and the driving circuit portion 504 are sealed between the element substrate 501 and the encapsulation substrate 506 by the sealing material 505.

In addition, on the element substrate 501, an external signal (for example, a video signal, a clock signal, a start signal, a reset signal, or the like) or a potential is transmitted to the driving circuit portion 503 and the driving circuit portion 504. Lead wires 507 are provided for connecting external input terminals. Here, an example in which an FPC (Flexible Print Circuit) 508 is provided as an external input terminal is shown. Although only the FPC is shown here, a printed wiring board (PWB) may be mounted on the FPC. The light emitting device of the present specification includes not only a light emitting device body but also a state in which an FPC or a PWB is attached thereto.

Next, the cross-sectional structure will be described with reference to Fig. 5B. The driver circuit portion and the pixel portion are formed on the element substrate 501. Here, the driver circuit portion 503 and the pixel portion 502, which are source line driving circuits, are shown.

The driver circuit section 503 has shown an example in which a CMOS circuit combining the n-channel TFT 509 and the p-channel TFT 510 is formed. In addition, the driving circuit unit may be formed of various CMOS circuits, PMOS circuits, or NMOS circuits formed of TFTs. In addition, although the driver integrated type which formed the drive circuit on the board | substrate was shown in this embodiment, it is not necessarily limited to this, It is also possible to form a drive circuit outside not on a board | substrate.

In addition, the pixel portion 502 includes a first electrode (anode) electrically connected to a switching TFT 511, a current control TFT 512, and a wiring (a source electrode or a drain electrode) of the current control TFT 512. It is formed by a plurality of pixels including 513. In addition, an insulator 514 is formed to cover an end portion of the first electrode (anode) 513. Here, it forms using positive photosensitive acrylic resin.

In addition, it is preferable that a curved surface having a curvature is formed at the upper end or the lower end of the insulator 514 in order to improve the coating property of the film laminated on the upper layer. For example, when positive type photosensitive acrylic resin is used as a material of the insulator 514, it is preferable to have the curved surface which has a curvature radius (0.2 micrometer-3 micrometers) in the upper end of the insulator 514. As the insulator 514, both a negative type that is insoluble in an etchant by photosensitive light or a positive type that is insoluble in an etchant by light can be used, and is not limited to an organic compound. For example, both silicon oxide and silicon oxynitride can be used.

On the first electrode (anode) 513, an EL layer 515 and a second electrode (cathode) 516 are laminated. The EL layer 515 is provided with at least a light emitting layer, and the light emitting layer contains a phosphorescent organic metal iridium complex. In addition to the light emitting layer, the EL layer 515 can be appropriately provided with a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a charge generation layer, and the like.

In addition, the light emitting element 517 is formed by the lamination structure of the first electrode (anode) 513, the EL layer 515, and the second electrode (cathode) 516. As the material used for the first electrode (anode) 513, the EL layer 515, and the second electrode (cathode) 516, the material shown in Embodiment 1 can be used. Although not shown here, the second electrode (cathode) 516 is electrically connected to an FPC 508 which is an external input terminal.

In addition, although only one light emitting element 517 is shown in the cross-sectional view shown in FIG. 5B, it is assumed that a plurality of light emitting elements are arranged in a matrix in the pixel portion 502. In the pixel portion 502, light emitting devices capable of obtaining three kinds of light emission (R, G, B) can be selectively formed to form light emitting devices capable of full color display. In addition, it is possible to implement a light emitting device capable of full color display by combining with a color filter.

Furthermore, the sealing substrate 506 is bonded to the element substrate 501 by the seal member 505 so that the light emitting element 517 is provided in the space 518 surrounded by the element substrate 501, the encapsulation substrate 506, and the seal member 505. One structure is shown. In addition, the space 518 may include not only the case where an inert gas (nitrogen, argon, etc.) is filled, but also the structure filled with the sealing material 505.

In addition, it is preferable to use an epoxy resin for the sealing material 505. In addition, these materials are preferably materials that do not permeate moisture or oxygen as much as possible. As the material used for the encapsulation substrate 506, a plastic substrate made of fiberglass-reinforced plastics (FRP), polyvinyl fluoride (PVF), polyester, acrylic, or the like can be used in addition to a glass substrate or a quartz substrate.

As described above, the light emitting device based on the active matrix phosphorescence emission can be obtained.

In addition, the structure shown in this embodiment can be used combining suitably the structure shown in other embodiment.

(Embodiment 6)

In this embodiment, an example of various electronic devices completed by using a light emitting device based on phosphorescence, which is an aspect of the present invention, will be described with reference to FIG.

Electronic devices employing light emitting devices, for example, television devices (also called television or television receivers), monitors for computers, digital cameras, digital video cameras, digital photo frames, mobile phones (also called mobile phones, mobile phone devices) ), A portable game machine, a portable information terminal, a sound reproducing apparatus, and a large game machine such as a paching nose machine. A specific example of these electronic devices is shown in FIG.

Fig. 6A shows an example of a television device. The television unit 7100 has a display portion 7103 built into the housing 7101. An image can be displayed by the display portion 7103 and a light emitting device can be used for the display portion 7103. In addition, the structure which supported the housing 7101 by the stand 7105 is shown here.

The operation of the television device 7100 can be performed by an operation switch provided in the housing 7101 or a separate remote controller manipulator 7110. The operation keys 7109 provided in the remote controller 7110 can perform channel or volume operations, and can manipulate images displayed on the display unit 7103. In addition, a display unit 7107 that displays information output from the remote control manipulator 7110 may be provided in the remote control manipulator 7110.

In addition, the television device 7100 includes a receiver, a modem, or the like. The receiver can perform general television broadcast reception, and furthermore, by connecting to a wired or wireless communication network through a modem, information communication in one direction (sender to receiver) or two-way (between the sender and receiver, or between receivers, etc.) can be performed. It is also possible to carry out.

6B is a computer, which includes a main body 7201, a housing 7202, a display portion 7203, a keyboard 7204, an external connection port 7205, a pointing device 7206, and the like. In addition, a computer is manufactured using the light emitting device for its display portion 7203.

FIG. 6C is a portable entertainment device, which is composed of two housings, a housing 7301 and a housing 7302, and is connected to the opening and closing by a connecting portion 7303. A display portion 7304 is built into the housing 7301, and a display portion 7305 is built into the housing 7302. In addition, the portable entertainment device shown in Fig. 6C is a speaker portion 7308, a recording medium insertion portion 7307, an LED lamp 7308, an input means (operation key 7309, a connection terminal 7310, Sensor 7311 (force, displacement, position, velocity, acceleration, angular velocity, revolutions, distance, light, liquid, magnetism, temperature, chemical, voice, time, hardness, electric field, current, voltage, power, radiation, flow rate , Humidity, inclination, vibration, odor or infrared rays), microphone 7312) and the like. Of course, the configuration of the portable entertainment device is not limited to the above-described one, and at least one of the display portion 7304 and the display portion 7305, or any one of the light emitting devices can be used, and other accessory equipment can be provided as appropriate. The portable entertainment apparatus shown in Fig. 6C has a function of reading a program or data recorded on a recording medium and displaying the information on the display unit, or performing wireless communication with other portable entertainment equipment to share information. In addition, the function of the portable entertainment device shown in FIG. 6C is not limited thereto and may have various functions.

6D shows an example of a mobile phone. The mobile telephone 7400 includes an operation button 7403, an external connection port 7404, a speaker 7405, a microphone 7406, and the like, in addition to the display portion 7402 built into the housing 7401. In addition, the cellular phone 7400 is manufactured using a light emitting device for the display portion 7402.

The mobile telephone 7400 shown in Fig. 6D can input information by touching the display portion 7402 with a finger or the like. In addition, operations such as making a phone call or composing an e-mail can be performed by touching the display portion 7402 with a finger or the like.

The display section 7402 mainly has three modes. The first is a display mode mainly for displaying images, and the second is an input mode mainly for inputting information such as text. The third is a display + input mode in which two modes, a display mode and an input mode, are mixed.

For example, when making a call or creating an e-mail, the display portion 7402 can be set to a text input mode for mainly inputting text, and the text input operation displayed on the screen can be performed. In this case, it is preferable to display a keyboard or number buttons on most of the screens of the display portion 7402.

In addition, by providing a detection device having a sensor for detecting an inclination such as a gyro or an acceleration sensor inside the mobile phone 7400, the direction (vertical or horizontal) of the mobile phone 7400 is determined to determine the screen of the display portion 7402. The display can be switched automatically.

In addition, switching of the screen mode is performed by touching the display portion 7402 or by operating the operation button 7403 of the housing 7401. It is also possible to switch by the kind of the image displayed on the display portion 7402. For example, if the image signal displayed on the display unit is video data, the display mode is switched. If the image signal is text data, the display mode is switched to the input mode.

In addition, in the input mode, a signal detected by the optical sensor of the display unit 7402 is detected, and when there is no input by a touch operation of the display unit 7402 for a certain period of time, the display mode is controlled to switch from the input mode to the display mode. It may be.

The display portion 7402 may function as an image sensor. For example, identity authentication can be performed by contacting the display portion 7402 with a palm or a finger and capturing a palm print, a fingerprint, or the like. Further, by using a backlight for emitting near infrared light or a sensing light source for emitting near infrared light, a finger vein, a palm vein, or the like can be captured.

The electronic device can be obtained by applying the light-emitting device which is one aspect of this invention by the above. The application range of the light emitting device is very wide, and it is possible to apply to electronic devices of all fields.

In addition, the structure shown in this embodiment can be used suitably combining with the structure shown in other embodiment.

(Seventh Embodiment)

In this embodiment, an example of a lighting device to which a light emitting device based on phosphorescence light emission, which is one embodiment of the present invention, is applied will be described with reference to FIG. 7.

7 shows an example in which a light emitting device is used as an indoor lighting device 8001. In addition, since the light emitting device can be made large, a large area lighting device can be formed. In addition, by using the housing having a curved surface, the illuminating device 8002 having the curved light emitting region can be formed. Since the light emitting element included in the light emitting device shown in this embodiment is a thin film type, the design freedom of the housing is high. Therefore, variously designed lighting devices can be formed. Furthermore, a large lighting apparatus 8003 may be provided on the wall of the room.

Further, by using the light emitting device on the surface of the table, the lighting device 8004 having a function as a table can be realized. In addition, by using the light emitting device for a part of the other furniture, the lighting device having a function as a furniture can be provided.

As described above, various lighting apparatuses to which the light emitting device is applied can be obtained. In addition, such a lighting device is to be included in one aspect of the present invention.

In addition, the structure shown in this embodiment can be used suitably combining with the structure shown in other embodiment.

In the present embodiment, the light emitting device 1 using the phosphorescent organometallic iridium complex [Ir (dptzn) ₂ (acac)] (formula (103)) in the light emitting layer will be described with reference to FIG. In addition, the chemical formula of the material used in the present Example is shown below.

<< Production of Light-Emitting Element 1 >>

First, indium tin oxide (ITSO) containing silicon oxide was formed on the glass substrate 1100 by sputtering to form a first electrode 1101 serving as an anode. In addition, the film thickness was 110 nm and the electrode area was 2 mm x 2 mm.

Subsequently, as a pretreatment for forming the light emitting device 1 on the substrate 1100, the surface of the substrate was washed with water and calcined at 200 ° C. for 1 hour, followed by UV ozone treatment for 370 seconds.

Subsequently, the substrate was introduced into a vacuum deposition apparatus whose pressure was reduced to about 10 ⁻⁴ Pa, and the substrate 1100 was left to cool for 30 minutes after vacuum firing at 170 ° C. for 30 minutes in a heating chamber of the vacuum deposition apparatus. It was.

Subsequently, the substrate 1100 was fixed to a holder provided in the vacuum deposition apparatus so that the surface on which the first electrode 1101 was formed was downward. In this embodiment, the hole injection layer 1111, the hole transport layer 1112, the light emitting layer 1113, the electron transport layer 1114, and the electron injection layer 1115, which constitute the EL layer 1102, are sequentially formed by vacuum deposition. The case will be described.

After depressurizing the inside of the vacuum apparatus to 10 ^-4 Pa, 1, 3, 5-tri (dibenzothiophen-4-yl) benzene (abbreviated as: DBT3P-II) and molybdenum oxide (VI) were converted into DBT3P-II (abbreviated as: The hole injection layer 1111 was formed on the first electrode 1101 by co-depositing so that the molybdenum oxide was 4: 2 (mass ratio). The film thickness was 40 nm. Co-deposition also refers to a deposition method in which a plurality of different materials are evaporated simultaneously from different evaporation sources.

Subsequently, 20 nm of 4-phenyl-4 '-(9-phenylfluoren-9-yl) triphenylamine (abbreviated as BPAFLP) was deposited to form a hole transport layer 1112.

Next, the light emitting layer 1113 was formed on the hole transport layer 1112. 2- [3- (dibenzothiophen-4-yl) phenyl] dibenzo [f, h] quinoxaline (abbreviated name: 2mDBTPDBq-II), 4, 4'-bis [N- (1-naphthyl)- N-phenylamino] biphenyl (abbreviated: NPB), (acetylacetonato) bis (2, 4-diphenyl-1, 3, 5-triazinato) iridium (III) (abbreviated: [Ir (dptzn) ₂ (acac)]) is co-deposited so that 2mDBTPDBq-II (abbreviated): NPB (abbreviated): [Ir (dptzn) ₂ (acac)] (abbreviated) = 0.8: 0.2: 0.01 (mass ratio) to emit light layer 1113 Formed. The film thickness was 40 nm.

Subsequently, 10 nm of 2- [3- (dibenzothiophen-4-yl) phenyl] dibenzo [f, h] quinoxaline (abbreviated as: 2 mDBTPDBq-II) was deposited on the light emitting layer 1113, followed by vasophenanthroline The electron transport layer 1114 was formed by depositing 20 nm (abbreviation: Bphen). Further, an electron injection layer 1115 was formed by depositing 1 nm of lithium fluoride on the electron transport layer 1114.

Finally, aluminum was deposited on the electron injection layer 1115 to have a film thickness of 200 nm to form a second electrode 1103 serving as a cathode, thereby obtaining Light-emitting Element 1. In addition, in the above-described deposition process, all of the depositions used resistance heating.

Table 1 shows the device structure of Light-emitting Element 1 obtained as described above.

In addition, the produced light emitting element 1 was sealed in a glove box in a nitrogen atmosphere so as not to be exposed to the atmosphere (the sealing material was applied around the element and heat-treated at 80 ° C. for 1 hour at the time of sealing).

<< Operating Characteristics of Light-Emitting Element 1 >>

The operation characteristics of the manufactured Light-emitting Element 1 were measured. In addition, the measurement was performed at room temperature (ambient maintained at 25 degreeC).

First, the luminance-current efficiency characteristics of Light-emitting Element 1 are shown in FIG. 9, the vertical axis represents current efficiency (cd / A) and the horizontal axis represents luminance (cd / m ² ). In addition, voltage-luminance characteristics of Light-emitting Element 1 are shown in FIG. 10. 10 shows luminance (cd / m ² ) on the vertical axis and voltage (V) on the horizontal axis. Also showed the main initial characteristic values of the light-emitting element 1 at 1000cd / m ² vicinity in Table 2 below.

Through the above results, it can be seen that the light emitting device 1 manufactured in the present embodiment exhibits high external quantum efficiency and thus high light emission efficiency. Furthermore, with regard to color purity, it can be seen that orange light emission with good purity is shown.

In addition, Fig. 11 shows the emission spectrum when a current was passed through the light emitting element at a current density of 25 mA / cm ² . As shown in Fig. 11, the emission spectrum of Light-emitting Element 1 has a peak at 583 nm, suggesting that it is derived from the emission of phosphorescent organometallic iridium complex [Ir (dptzn) ₂ (acac)] (abbreviated).

In the present Example, the light emitting element 2 using the phosphorescent organometallic iridium complex [Ir (dppm) ₂ (acac)] (structure (100)) was manufactured, and the operation characteristic and reliability were measured. In addition, the light emitting device 2 prepared in the present Example is 2- [3 ′-(dibenzothiophen-4-yl) biphenyl-3-yl] di instead of 2mDBTPDBq-II used in the light emitting layer and the electron transporting layer of Example 1. 4, 4′-di (1-naphthyl) -4 ′-(9-phenyl instead of NPB used in the light emitting layer of Example 1, using benzo [f, h] quinoxaline (abbreviated name: 2mDBTBPDBq-II) -9H-carbazol-3-yl) triphenylamine (abbreviated as: PCBNBB) can be prepared in the same manner as in the light emitting device 1 prepared in Example 1 except that the mass ratio is slightly different. Description will be made with reference to Example 1, and description is omitted. In addition, the structural formula of the substance newly used in the present Example is shown below.

Table 3 below shows the device structure of Light-emitting Element 2 manufactured in this example.

<< Operating Characteristics of Light-Emitting Element 2 >>

The operation characteristics of the manufactured light emitting device 2 were measured. In addition, the measurement was performed at room temperature (ambient maintained at 25 degreeC).

First, the luminance-current efficiency characteristics of Light-emitting Element 2 are shown in FIG. 16, the vertical axis represents current efficiency (cd / A) and the horizontal axis represents luminance (cd / m ² ). In addition, voltage-luminance characteristics of Light-emitting Element 2 are shown in FIG. 17. 17 shows luminance (cd / m ² ) on the vertical axis and voltage (V) on the horizontal axis. In addition, the main initial characteristic value of the light emitting element 2 in the vicinity of 1000 cd / m ² is shown in Table 4 below.

Through the above results, it can be seen that the light emitting device 2 manufactured in the present embodiment shows high external quantum efficiency and thus high light emission efficiency. Furthermore, with regard to color purity, it can be seen that orange light emission with good purity is shown.

Moreover, the light emission spectrum when the electric current is passed through the light emitting element 2 at the current density of 25 mA / cm <^2> is shown in FIG. As shown in FIG. 18, the emission spectrum of the light emitting element 2 has a peak at 591 nm, suggesting that it originates in the light emission of the phosphorescent organometallic iridium complex [Ir (dppm) ₂ (acac)].

In addition, the results of the reliability test for the light emitting element 2 is shown in FIG. In Fig. 19, the vertical axis represents normalized luminance (%) when the initial luminance is 100%, and the horizontal axis represents drive time (h) of the device. In addition, the reliability test set the initial luminance to 5000 cd / m ² and ran the light emitting element 2 under the condition of a constant current density. As a result, the luminance after 1700 hours of the light emitting element 2 maintained about 90% of the initial luminance.

Therefore, it was found that the light emitting element 2 exhibits high reliability. In addition, it was found that a long-life light emitting device can be obtained by using the phosphorescent organometallic iridium complex of the present invention for a light emitting device.

In this embodiment, Light-Emitting Element 3 using the phosphorescent organometallic iridium complex [Ir (tBuppm) ₂ (acac)] (structure (105)) was manufactured and measured for its operation characteristics and reliability. In addition, the light emitting device 3 manufactured in the present embodiment can be manufactured in the same manner as the light emitting device 1 manufactured in Example 1 except that some of the materials used for the light emitting layer and the electron transporting layer, the mass ratio, and the film thickness thereof are different. Therefore, the description of the manufacturing method will be referred to Example 1, and description thereof will be omitted.

Table 5 below shows the device structure of the light emitting device 3 manufactured in the present embodiment.

<< Operating Characteristics of Light-Emitting Element 3 >>

The operation characteristics of the manufactured light emitting device 3 were measured. In addition, the measurement was performed at room temperature (ambient maintained at 25 degreeC).

First, the luminance-current efficiency characteristic of Light-emitting Element 3 is shown in FIG. In addition, in FIG. 20, the vertical axis represents current efficiency (cd / A), and the horizontal axis represents luminance (cd / m ² ). In addition, voltage-luminance characteristics of Light-emitting Element 3 are shown in FIG. 21. 21 shows luminance (cd / m ² ) on the vertical axis and voltage (V) on the horizontal axis. In addition, the main initial characteristic value of the light emitting element 3 in the vicinity of 1000 cd / m ² is shown in Table 6 below.

Through the above results, it can be seen that the light emitting device 3 manufactured in the present embodiment exhibits high external quantum efficiency and thus high light emission efficiency. Furthermore, with regard to color purity, it can be seen that green light emission with good purity is shown.

Moreover, the light emission spectrum at the time of flowing an electric current through the current density of 25 mA / cm <^{2> in} the light emitting element 3 is shown in FIG. As shown in FIG. 22, the light emission spectrum of the light emitting element 3 has a peak at 548 nm, suggesting that it originates in light emission of the phosphorescent organometallic iridium complex [Ir (tBuppm) ₂ (acac)].

In addition, the results of the reliability test for the light emitting element 3 is shown in FIG. In Fig. 23, the vertical axis represents normalized luminance (%) when the initial luminance is 100%, and the horizontal axis represents drive time (h) of the device. In addition, the reliability test set the initial luminance to 5000cd / m ² and drive the light emitting element 3 under the condition of a constant current density. As a result, the luminance after 300 hours of the light emitting element 3 was maintained at about 90% of the initial luminance.

Therefore, it was found that the light emitting element 3 exhibits high reliability. In addition, it was found that a long-life light emitting device can be obtained by using the phosphorescent organometallic iridium complex of the present invention for a light emitting device.

In the present embodiment, the light emitting device 4 shown in Fig. 30 using the phosphorescent organometallic iridium complex [Ir (tBuppm) ₂ (acac)] (structural formula (105)) was manufactured and measured for its operating characteristics and reliability. It was. In addition, the light emitting element 4 manufactured in the present embodiment is a light emitting element (hereinafter, referred to as a tandem light emitting element) having a structure having a plurality of EL layers interposed therebetween as described in the third embodiment. In addition, the chemical formula of the material used in the present Example is shown below.

<< Production of Light-Emitting Element 4 >>

First, indium tin oxide (ITSO) containing silicon oxide was formed on the glass substrate 3000 by sputtering to form a first electrode 3001 functioning as an anode. In addition, the film thickness was 110 nm and the electrode area was 2 mm x 2 mm.

Subsequently, as a pretreatment for forming the light emitting device 4 on the substrate 3000, the surface of the substrate was washed with water, fired at 200 ° C for 1 hour, and then subjected to UV ozone treatment for 370 seconds.

Subsequently, the substrate was introduced into a vacuum deposition apparatus whose pressure was reduced to about 10 ⁻⁴ Pa and subjected to vacuum baking at 170 ° C. for 30 minutes in a heating chamber of the vacuum deposition apparatus, and then the substrate 3000 was left to cool for about 30 minutes.

Subsequently, the substrate 3000 was fixed to the holder provided in the vacuum deposition apparatus so that the surface on which the first electrode 3001 was formed was lowered. In the present embodiment, the first hole injection layer 3011a, the first hole transport layer 3012a, the first light emitting layer 3013a, and the first electron transport layer 3014a constitute the first EL layer 3002a by vacuum deposition. , The first electron injection layer 3015a is sequentially formed, and then the first charge generation layer is formed, followed by the second hole injection layer 3011b and the second hole transport layer 3012b constituting the second EL layer 3002b. A third charge generating layer is formed after forming the second light emitting layer 3013b, the second electron transporting layer 3014b, and the second electron injection layer 3015b, and then forming a third EL layer 3002c. A case of forming the hole injection layer 3011c, the third hole transport layer 3012c, the third light emitting layer 3013c, the third electron transport layer 3014c, and the third electron injection layer 3015c will be described.

After depressurizing the inside of the vacuum apparatus to 10 ^-4 Pa, 1, 3, 5-tri (dibenzothiophen-4-yl) benzene (abbreviated as: DBT3P-II) and molybdenum oxide (VI) were converted into DBT3P-II (abbreviated as: ): The first hole injection layer 3011a was formed on the first electrode 3001 by co-deposition so that molybdenum oxide = 1: 0.5 (mass ratio). The film thickness was 26.6 nm. In addition, co-deposition is a deposition method in which a plurality of different materials are simultaneously evaporated from different evaporation sources.

Subsequently, 20 nm of 4-phenyl-4 '-(9-phenylfluoren-9-yl) triphenylamine (abbreviated as BPAFLP) was deposited to form a first hole transport layer 3012a.

Subsequently, a first light emitting layer 3013a was formed on the first hole transport layer 3012a. 2- [3 ′-(dibenzothiophen-4-yl) biphenyl-3-yl] dibenzo [f, h] quinoxaline (abbreviated: 2mDBTBPDBq-II), 4, 4′-di (1-naph Tyl) -4 '-(9-phenyl-9H-carbazol-3-yl) triphenylamine (abbreviated as: PCBNBB), bis (2, 3, 5-triphenylpyrazinato) (dipivaroylmethanato) ) Iridium (III) (abbreviated: [Ir (tppr) ₂ (dpm)]), 2mDBTBPDBq-II (abbreviated): PCBNBB (abbreviated): [Ir (tppr) ₂ (dpm)] (abbreviated) = 0.8: 0.2 The first light emitting layer 3013a was formed by co-depositing to be 0.06 (mass ratio). The film thickness was 40 nm.

Subsequently, 5 nm of 2mDBTPDBq-II (abbreviated) was deposited on the first light emitting layer 3013a, followed by vapor deposition of vasophenanthroline (abbreviated as Bphen) by 10 nm to form the first electron transport layer 3014a. Further, the first electron injection layer 3015a was formed by depositing 0.1 nm of lithium oxide (Li ₂ O) on the first electron transport layer 3014a.

Subsequently, on the first electron injection layer 3015a, copper phthalocyanine (abbreviated as CuPc) was deposited at a thickness of 2 nm to form the first charge generation layer 3016a.

Next, the second hole injection layer is co-deposited on the first charge generation layer 3016a so that DBT3P-II (abbreviated) and molybdenum oxide (VI) are DBT3P-II (abbreviated): molybdenum oxide = 0.5: 0.5 (mass ratio). 3011b was formed. The film thickness was 3.3 nm.

Subsequently, a second hole transport layer 3012b was formed by depositing 9- [4- (9-phenylcarbazol-3-yl)] phenyl-10-phenylanthracene (abbreviated as: PCzPA) by 10 nm.

Subsequently, a second light emitting layer 3013b was formed on the second hole transport layer 3012b. CzPA (abbreviated), N, N′-bis (3-methylphenyl) -N, N′-bis [3- (9-phenyl-9H-fluoren-9-yl) phenyl] pyrene-1, 6-diamine ( Abbreviated name: 1,6mMemFLPAPrn) was co-deposited so that CzPA (abbreviated): 1,6mMemFLPAPrn (abbreviated) = 1: 0.05 (mass ratio), and the 2nd light emitting layer 3013b was formed. The film thickness was 30 nm.

Subsequently, 5 nm of CzPA (abbreviated) was deposited on the second light emitting layer 3013b, and then 10 nm of Bphen (abbreviated) was deposited to form a second electron transport layer 3014b. Further, the second electron injection layer 3015b was formed by depositing 0.1 nm of lithium oxide (Li ₂ O) on the second electron transport layer 3014b.

Subsequently, a second charge generation layer 3016b was formed by depositing copper phthalocyanine (abbreviated as CuPc) at a thickness of 2 nm on the second electron injection layer 3015b.

Next, the third hole injection layer is co-deposited on the second charge generation layer 3016b so that DBT3P-II (abbreviated) and molybdenum oxide (VI) are DBT3P-II (abbreviated): molybdenum oxide = 1: 0.5 (mass ratio). (3011c) was formed. The film thickness was 50 nm.

Subsequently, a third hole transport layer 3012c was formed by depositing 20 nm of BPAFLP (abbreviated).

Subsequently, a third light emitting layer 3013c was formed on the third hole transport layer 3012c. 2 mDBTBPDBq-II (abbreviated), PCBNBB (abbreviated), (acetylacetonato) bis (6-tert-butyl-4-phenylpyrimidinato) iridium (III) (abbreviated as: [Ir (tBuppm) ₂ (acac)]) 2mDBTBPDBq-II (abbreviated): PCBNBB (abbreviated): [Ir (tBuppm) ₂ (acac)] = 0.8: 0.2: 0.06 (mass ratio) by co-depositing at a film thickness of 30 nm, followed by 2mDBTBPDBq-II (abbreviated) , PCBNBB (abbreviated), [Ir (dppm) ₂ (acac)] (abbreviated) to 2mDBTBPDBq-II (abbreviated): PCBNBB (abbreviated): [Ir (dppm) ₂ (acac)] = 0.8: 0.2: 0.06 (mass ratio ), The third light emitting layer 3013c was formed by co-depositing at a film thickness of 10 nm.

Subsequently, 15 nm of 2mDBTPDBq-II (abbreviated) was deposited on the 3rd light emitting layer 3013c, and Bphen (abbreviated) was deposited by 15 nm, and the 3rd electron carrying layer 3014c was formed. Further, the third electron injection layer 3015c was formed by depositing 1 nm of lithium fluoride (LiF) on the third electron transport layer 3014c.

Finally, aluminum was deposited on the third electron injection layer 3015c so as to have a thickness of 200 nm to form a second electrode 3003 serving as a cathode, thereby obtaining Light-emitting Element 4. In addition, in the above-described deposition process, all of the depositions used resistance heating.

Table 7 shows the device structure of Light-emitting Element 4 obtained as described above.

In addition, the produced light emitting element 4 was sealed in a glove box in a nitrogen atmosphere so as not to be exposed to the atmosphere (the sealant was applied around the element and heat-treated at 80 ° C. for 1 hour at the time of sealing).

<< Operating Characteristics of Light-Emitting Element 4 >>

The operation characteristics of the manufactured light emitting device 4 were measured. In addition, the measurement was performed at room temperature (ambient maintained at 25 degreeC).

First, the luminance-current efficiency characteristics of Light-emitting Element 4 are shown in FIG. In FIG. 24, the vertical axis represents current efficiency (cd / A), and the horizontal axis represents luminance (cd / m ² ). In addition, voltage-luminance characteristics of Light-emitting Element 4 are shown in FIG. 25. In addition, in FIG. 25, luminance (cd / m ² ) is represented on the vertical axis and voltage (V) on the horizontal axis. In addition, the main initial characteristic values of the light emitting element 4 in the vicinity of 1000 cd / m ² are shown in Table 8 below.

Through the above results, it can be seen that the light emitting device 4 manufactured in the present embodiment shows high external quantum efficiency and thus high light emission efficiency. Furthermore, it can be seen from the chromaticities (x, y) that the color temperature shows about 3000K of yellowish white light emission (bulb color).

Moreover, the light emission spectrum when the current is made to flow through the light emitting element 4 at a current density of 25 mA / cm ² is shown in FIG. 26. As shown in FIG. 26, the light emission spectrum of the light emitting element 4 has peaks at 470 nm, 549 nm, and 618 nm, respectively, suggesting that it is derived from the light emission of the phosphorescent organometallic iridium complex contained in each light emitting layer. Moreover, the average color rendering index (Ra) calculated from this spectrum was 90, and showed very high color rendering property.

In addition, the results of the reliability test for the light emitting element 4 is shown in FIG. In Fig. 27, the vertical axis represents normalized luminance (%) when the initial luminance is 100%, and the horizontal axis represents drive time (h) of the device. In addition, the reliability test set the initial luminance to 5000 cd / m ² and ran the light emitting element 4 under the condition of a constant current density. As a result, the luminance after 120 hours of the light emitting element 4 maintained about 96% of the initial luminance.

Therefore, it was found that the light emitting element 4 exhibits high reliability. In addition, it was found that a long-life light emitting device can be obtained by using the phosphorescent organometallic iridium complex of the present invention for a light emitting device.

(Reference example)

Below, the synthesis | combining method of the phosphorescent organometallic iridium complex used in the present Example is demonstrated.

<< synthesis example 1 >>

In Synthesis Example 1, the organometallic complex, (acetylacetonato) bis (4, 6-diphenylpyrimidinato) iridium (III), which is one embodiment of the present invention represented by Structural Formula (100) of Embodiment 1 (abbreviated as: [Ir ( dppm) ₂ (acac)]) specifically exemplifies. In addition, the structure of [Ir (dppm) ₂ (acac)] is shown below.

&Lt; Step 1; Synthesis of 4, 6-diphenylpyrimidine (abbreviated: Hdppm)>

First, 5.02 g of 4, 6-dichloropyrimidine, 8.29 g of phenylboronic acid, 7.19 g of sodium carbonate, bis (triphenylphosphine) palladium (II) dichloride (abbreviated as: Pd (PPh ₃ ) ₂ Cl ₂ ) 0.29 g, 20 mL of water and 20 mL of acetonitrile were placed in an eggplant flask with a reflux tube, and the inside was argon-substituted. The reaction vessel was heated by irradiating microwave (2.45 GHz 100W) for 60 minutes. 2.08 g of phenylboronic acid, 1.79 g of sodium carbonate, 0.070 g of Pd (PPh ₃ ) ₂ Cl ₂ , 5 mL of water, and 5 mL of acetonitrile were further added to the flask and heated by irradiation with microwave (2.45 GHz 100 W) for 60 minutes. Then water was added to this solution and the organic layer was extracted with dichloromethane. The obtained extract was washed with water and dried over magnesium sulfate. The solution after drying was filtered. After distilling off the solvent of this solution, the obtained residue was purified by silica gel column chromatography using dichloromethane as a developing solvent to obtain pyrimidine derivative Hdppm (yellow white powder, yield 38%). In addition, the irradiation of microwaves used the microwave synthesizer (Discover made by CEM). The synthesis scheme (a-1) of step 1 is shown below.

&Lt; Step 2; Di-μ-chloro-bis [bis (4,6-diphenylpyrimidinato) iridium (III)] (abbreviated as: Synthesis of [Ir (dppm) ₂ Cl] ₂ )>

Subsequently, 15 mL of 2-ethoxyethanol, 5 mL of water, 1.10 g of Hdppm obtained in Step 1, and 0.69 g of iridium chloride hydrate (IrCl ₃ -H ₂ O) were placed in a branch flask with a reflux tube, and the inside of the branch flask was substituted with argon. I was. Thereafter, microwaves (2.45 GHz 100 W) were irradiated for 1 hour to react. After distilling off the solvent, the obtained residue was filtered with ethanol and then washed to obtain a heteronuclear complex [Ir (dppm) ₂ Cl] ₂ (reddish brown powder, yield 88%). The synthesis scheme (a-2) of step 2 is shown below.

&Lt; Step 3; Synthesis of (acetylacetonato) bis (4,6-diphenylpyrimidinato) iridium (III) (abbreviated as: [Ir (dppm) ₂ (acac)])

Further, 40 mL of 2-ethoxyethanol, 1.44 g of [Ir (dppm) ₂ Cl] ₂ obtained in Step 2, 0.30 g of acetylacetone, and 1.07 g of sodium carbonate were placed in a eggplant flask with a reflux tube, and the inside of the eggplant flask was substituted with argon. I was. Thereafter, microwaves (2.45 GHz 100 W) were irradiated for 60 minutes to react. The residue obtained by distilling off the solvent was dissolved in dichloromethane and filtered to remove insoluble matters. The filtrate obtained was washed with water, followed by saturated brine and dried over magnesium sulfate. The solution after drying was filtered. After distilling off the solvent of this solution, the obtained residue was purified by silica gel column chromatography using dichloromethane: ethyl acetate = 50: 1 (volume ratio) as a developing solvent. Thereafter, recrystallized with a mixed solvent of dichloromethane and hexane to give the target orange powder (yield 65%). The synthesis scheme (a-3) of step 3 is shown below.

The result of analysis by nuclear magnetic resonance spectroscopy ( ¹ H-NMR) of the orange powder obtained in the step 3 is shown below. In addition, a ¹ H-NMR chart is shown in FIG. 12. From this result, it was understood that in Synthesis Example 1, the phosphorescent organometallic iridium complex represented by Structural Formula (100) (Ir (dppm) ₂ (acac)) was obtained.

¹ H-NMR. δ (CDCl ₃ ): 1.83 (s, 6H), 5.29 (s, 1H), 6.48 (d, 2H), 6.80 (t, 2H), 6.90 (t, 2H), 7.55-7.63 (m, 6H), 7.77 (d, 2H), 8.17 (s, 2H), 8.24 (d, 4H), 9.17 (s, 2H).

<< synthesis example 2 >>

In Synthesis Example 2, (acetylacetonato) bis (6-methyl-4-phenylpyrimidinato) iridium (III) which is a phosphorescent organometallic iridium complex represented by Structural Formula (101) of Embodiment 1 (abbreviated as: [Ir (mppm) ) ₂ (acac)]) specifically exemplifies. In addition, the structure of [Ir (mppm) ₂ (acac)] is shown below.

&Lt; Step 1; Synthesis of 4-methyl-6-phenyl pyrimidine (abbreviated as Hmppm)>

First, 4.90 g of 4-chloro-6-methyl pyrimidine, 4.80 g of phenylboronic acid, 4.03 g of sodium carbonate, bis (triphenylphosphine) palladium (II) dichloride (abbreviated as: Pd (PPh ₃ ) ₂ Cl ₂ ) 0.16 g, 20 mL of water, and 10 mL of acetonitrile were placed in an eggplant flask with a reflux tube, and the inside was argon-substituted. The reaction vessel was heated by irradiating microwave (2.45 GHz 100W) for 60 minutes. Further here, 2.28 g of phenylboronic acid, 2.02 g of sodium carbonate, Pd (PPh ₃ ) ₂ Cl ₂ 0.082 g, 5 mL of water, and 10 mL of acetonitrile were placed in a flask, and heated again by irradiating microwave (2.45 GHz 100 W) for 60 minutes. Water was then added to this solution and extracted with dichloromethane. The obtained extract was washed with saturated aqueous sodium carbonate solution, water, and then brine, and dried over magnesium sulfate. The solution after drying was filtered. After distilling off the solvent of this solution, the obtained residue was purified by silica gel column chromatography using dichloromethane: ethyl acetate = 9: 1 (volume ratio) as a developing solvent to obtain the target pyrimidine derivative Hmppm (orange oily substance). , Yield 46%). In addition, the irradiation of microwaves used the microwave synthesizer (Discover made by CEM). The synthesis scheme (b-1) of step 1 is shown below.

&Lt; Step 2; Di-μ-chloro-bis [bis (6-methyl-4-phenylpyrimidinato) iridium (III)] (abbreviated as: Synthesis of [Ir (mppm) ₂ Cl] ₂ )>

Subsequently, 15 mL of 2-ethoxyethanol, 5 mL of water, 1.51 g of Hmppm obtained in Step 1, and 1.26 g of iridium chloride hydrate (IrCl ₃ -H _{2 O} ) were placed in an eggplant flask with a reflux tube and argon-substituted inside the eggplant flask. . Thereafter, microwaves (2.45 GHz 100 W) were irradiated for 1 hour to react. After distilling off the solvent, the obtained residue was washed with ethanol and filtered to obtain a heteronuclear complex [Ir (mppm) ₂ Cl] ₂ (dark green powder, yield 77%). The synthesis scheme of the step 2 is shown below.

&Lt; Step 3; Synthesis of (acetylacetonato) bis (6-methyl-4-phenylpyrimidinato) iridium (III) (abbreviated as: [Ir (mppm) ₂ (acac)])

Further, 40 mL of 2-ethoxyethanol, 1.84 g of the heteronuclear complex [Ir (mppm) ₂ Cl] ₂ obtained in Step 2, 0.48 g of acetylacetone, and 1.73 g of sodium carbonate were placed in a eggplant flask with a reflux tube, and the inside of the eggplant flask was placed. Argon substitution. Thereafter, microwaves (2.45 GHz 100 W) were irradiated for 60 minutes to react. The solvent was distilled off and the obtained residue was dissolved in dichloromethane and filtered to remove insoluble matters. The obtained filtrate was washed with water, followed by saturated brine, and dried over magnesium sulfate. The solution after drying was filtered. After distilling off the solvent of this solution, the obtained residue was purified by silica gel column chromatography using dichloromethane: ethyl acetate = 4: 1 (volume ratio) as a developing solvent. Thereafter, the target product was obtained as a yellow powder by recrystallization with a mixed solvent of dichloromethane and hexane (yield 44%). The synthesis scheme (b-3) of step 3 is shown below.

It is given in the analysis result by nuclear magnetic resonance spectroscopy ⁽¹ H-NMR) as a yellow powder obtained in the step 3. In addition, a ¹ H-NMR chart is shown in FIG. 13. From this result, it was found that in Synthesis Example 2, the phosphorescent organometallic iridium complex represented by Structural Formula (101) [Ir (mppm) ₂ (acac)] was obtained.

¹ H-NMR. δ (CDCl ₃ ): 1.78 (s, 6H), 2.81 (s, 6H), 5.24 (s, 1H), 6.37 (d, 2H), 6.77 (t, 2H), 6.85 (t, 2H), 7.61- 7.63 (m, 4H), 8.97 (s, 2H).

<< synthesis example 3 >>

In Synthesis Example 3, tris (4, 6-diphenylpyrimidinato) iridium (III) (abbreviated as: [Ir (dppm) ₃ ]), which is a phosphorescent organometallic iridium complex represented by Structural Formula (102) of Embodiment 1 A synthesis example is illustrated concretely. In addition, the structure of [Ir (dppm) ₃ ] is shown below.

1.17 g of ligand Hdppm and 0.49 g of tris (acetylacetonato) iridium (III) obtained in Step 1 of Synthesis Example 1 were placed in a reaction vessel with three bangkok, and argon was substituted in the reaction vessel. Then, it heated and reacted at 250 degreeC for 45.5 hours. The reaction was dissolved in dichloromethane and the solution was filtered. The solvent of the obtained filtrate was distilled off and purified by silica gel column chromatography. Dichloromethane and then ethyl acetate were used as a developing solvent. The solvent of the obtained fraction was distilled off to obtain a red solid (yield 41%). The obtained solid was recrystallized with a mixed solvent of dichloromethane and hexane to obtain a red powder as a target product (yield 11%). The synthesis scheme (c-1) of Synthesis Example 3 is shown below.

It is given in the analysis result by nuclear magnetic resonance spectroscopy ⁽¹ H-NMR) of the red powder obtained in the above. In addition, a ¹ H-NMR chart is shown in FIG. 14. From this result, it was understood that in Synthesis Example 3, the phosphorescent organometallic iridium complex [Ir (dppm) 3] represented by Structural Formula (102) was obtained.

¹ H-NMR. δ (CDCl ₃ ): 6.88-7.04 (m, 9H), 7.51-7.54 (m, 9H), 7.90 (d, 3H), 8.07 (d, 3H), 8.09 (d, 3H), 8.21 (s, 3H ), 8.46 (s, 3 H).

<< synthesis example 4 >>

In Synthesis Example 4, (acetylacetonato) bis (2, 4-diphenyl-1, 3, 5-triazinato) iridium (III) which is a phosphorescent organometallic iridium complex represented by Structural Formula (103) of Embodiment 1 Examples of the synthesis of (abbreviated as: [Ir (dptzn) ₂ (acac)]) are specifically illustrated. In addition, the structure of [Ir (dptzn) ₂ (acac)] (abbreviated) is shown below.

&Lt; Step 1; Synthesis of 2, 4-diphenyl-1, 3, 5-triazine (abbreviated as: Hdptzn)>

First, 9.63 g of benzamidine hydrochloride and 10.19 g of Gold reagent (nickname: (dimethylaminomethyleneaminomethylene) dimethylammonium chloride, manufactured by Sigma-Aldrich) were placed in a flask and nitrogen-substituted. The reaction vessel was heated and reacted at 120 ° C. for 3 hours. Water was added to the reaction solution and filtered. The obtained product was washed with methanol to obtain the desired triazine derivative Hdptzn (abbreviated) (white powder, yield 30%). The synthesis scheme of step 1 is shown in (d-1) below.

&Lt; Step 2; Di-μ-chloro-bis [bis (2, 4-diphenyl-1, 3, 5-triazinato) iridium (III)] (abbreviated as: Synthesis of [Ir (dptzn) ₂ Cl] ₂ )>

Subsequently, 15 mL of 2-ethoxyethanol, 5 mL of water, 2.51 g of Hdptzn (abbreviated) obtained in Step 1, and 1.18 g of iridium chloride hydrate (IrCl ₃ -H ₂ O) were placed in a branch flask with a reflux tube, and the inside of the flask was placed. Argon substitution. Thereafter, microwaves (2.45 GHz 100 W) were irradiated for 30 minutes to react. The reaction solution was filtered and the obtained product was washed with ethanol to obtain a heteronuclear complex [Ir (dptzn) ₂ Cl] ₂ (abbreviated) (brown powder, yield 44%). The synthesis scheme of step 2 is shown in (d-2) below.

&Lt; Step 3; Synthesis of (acetylacetonato) bis (2,4-diphenyl-1,3,5-triazinato) iridium (III) (abbreviated as: [Ir (dptzn) ₂ (acac)])

Furthermore, 20 mL of 2-ethoxyethanol, 1.21 g of the heteronuclear complex [Ir (dptzn) ₂ Cl] ₂ (abbreviated) obtained in the step 2), 0.27 mL of acetylacetone, and 0.92 g of sodium carbonate were placed in an eggplant flask with a reflux tube, and the flask was Argon substitution inside. Thereafter, microwaves (2.45 GHz 100 W) were irradiated for 30 minutes to react. After dichloromethane was added to the reaction solution and the filtrate was distilled off, the solvent of the filtrate was distilled off. Then, the obtained residue was subjected to flash column chromatography (silica gel) using a mixed solvent of hexane and dichloromethane (volume ratio 1/25) as a developing solvent. The product was purified with to give a phosphorescent organometallic iridium complex [Ir (dptzn) ₂ (acac)] (abbreviated) as an orange powder (yield 10%). The synthesis scheme of step 3 is shown below (d-3).

The result of analysis by nuclear magnetic resonance spectroscopy ( ¹ H-NMR) of the orange powder obtained in the step 3 is shown below. In addition, a ¹ H-NMR chart is shown in FIG. 15. From this result, it was found that in Synthesis Example 4, the phosphorescent organometallic iridium complex represented by Structural Formula (103) described above (Ir (dptzn) ₂ (acac)) was obtained.

¹ H-NMR. δ (CDCl ₃ ): 1.85 (s, 6H), 5.31 (s, 1H), 6.56 (dd, 2H), 6.88-6.99 (m, 4H), 7.58-7.68 (m, 6H), 8.23 (dd, 2H ), 8.72 (dd, 4H), 9.13 (s, 2H).

<< synthesis example 5 >>

In Synthesis Example 5, (acetylacetonato) bis (6-tert-butyl-4-phenylpyrimidinato) iridium (III) which is a phosphorescent organometallic iridium complex represented by Structural Formula (105) of Embodiment 1 (abbreviated as: [ A synthesis example of Ir (tBuppm) ₂ (acac)]) is specifically illustrated. In addition, the structure of [Ir (tBuppm) ₂ (acac)] (abbreviated) is shown below.

&Lt; Step 1; Synthesis of 4-tert-butyl-6-phenylpyrimidine (abbreviated as HtBuppm)>

First, 22.5 g of 4, 4-dimethyl-1-phenylpentane-1, 3-dione and 50 g of formamide were placed in a eggplant flask with a reflux tube and nitrogen-substituted inside. By heating the reaction vessel, the reaction solution was refluxed for 5 hours. Thereafter, the solution was poured into an aqueous sodium hydroxide solution, and the organic layer was extracted with dichloromethane. The obtained organic layer was washed with water and brine, and dried over magnesium sulfate. The solution after drying was filtered. After distilling off the solvent of this solution, the obtained residue was purified by silica gel column chromatography using hexane: ethyl acetate = 10: 1 (volume ratio) as a developing solvent to obtain a pyrimidine derivative HtBuppm (colorless oily substance, yield 14). %). The synthesis scheme of step 1 is shown in (e-1) below.

&Lt; Step 2; Di-μ-chloro-bis [bis (6-tert-butyl-4-phenylpyrimidinato) iridium (III)] (abbreviated as: Synthesis of [Ir (tBuppm) ₂ Cl] ₂ )>

Subsequently, 15 mL of 2-ethoxyethanol, 5 mL of water, 1.49 g of HtBuppm obtained in Step 1, and 1.04 g of iridium chloride hydrate (IrCl ₃ -H ₂ O) were placed in a branch flask with a reflux tube, and argon substituted in the flask. . Thereafter, microwaves (2.45 GHz 100 W) were irradiated for 1 hour to react. After distilling off the solvent, the obtained residue was suction filtered and washed with ethanol to obtain a heteronuclear complex [Ir (tBuppm) ₂ Cl] ₂ (yellow green powder, yield 73%). The synthesis scheme of step 2 is shown in (e-2) below.

&Lt; Step 3; (Acetylacetonato) bis (6-tert-butyl-4-phenylpyrimidinato) iridium (III) (abbreviated as: Synthesis of [Ir (tBuppm) ₂ (acac)]>

Further, 40 mL of _2- ethoxyethanol, 1.61 g of the heteronuclear complex [Ir (tBuppm) ₂ Cl] ₂ obtained in Step 2, 2,3.1 g of acetylacetone, and 1.27 g of sodium carbonate were placed in an eggplant flask with a reflux tube and argon inside the flask. Substituted. Thereafter, microwaves (2.45 GHz 100 W) were irradiated for 60 minutes to react. The solvent was distilled off, and the obtained residue was suction filtered with ethanol and washed with water and ethanol. This solid was dissolved in dichloromethane and filtered through a filter aid laminated in the order of celite (Wako Pure Chemical Industries, Ltd., catalog number: 537-02305), alumina and celite. The solid obtained by distilling off the solvent was recrystallized with a mixed solvent of dichloromethane and hexane to obtain the target product as a yellow powder (yield 68%). The synthesis scheme of step 3 is shown in (e-3) below.

It is given in the analysis result by nuclear magnetic resonance spectroscopy ⁽¹ H-NMR) as a yellow powder obtained in the step 3. In addition, a ¹ H-NMR chart is shown in FIG. 28. From this result, in the synthesis example 5, it turned out that the phosphorescent organometallic iridium complex represented by Structural formula (105) [Ir (tBuppm) ₂ (acac)] is obtained.

¹ H-NMR. δ (CDCl ₃ ): 1.50 (s, 18H), 1.79 (s, 6H), 5.26 (s, 1H), 6.33 (d, 2H), 6.77 (t, 2H), 6.85 (t, 2H), 7.70 ( d, 2H), 7.76 (s, 2H), 9.02 (s, 2H).

<< synthesis example 6 >>

In Synthesis Example 6, N, N′-bis (3-methylphenyl) -N, N′-bis [3- (9-phenyl-9H-fluoren-9-yl) phenyl] pyrene- used in Example 4 The synthesis example of 1, 6- diamine (abbreviation: 1,6mMemFLPAPrn) is illustrated concretely. In addition, the structure of 1,6mMemFLPAPrn (abbreviated-name) is shown below.

<Step 1: Synthesis of 3-methylphenyl-3- (9-phenyl-9H-fluoren-9-yl) phenylamine (abbreviated as mMemFLPA)>

3.2 g (8.1 mmol) of 9- (3-bromophenyl) -9-phenylfluorene and 2.3 g (24.1 mmol) of sodium tert-butoxide were placed in a 200 mL three-necked flask and nitrogen-substituted in the flask. To this mixture was added 40.0 mL of toluene, 0.9 mL (8.3 mmol) of m-toluidine, and 0.2 mL of a 10% hexane solution of tri (tert-butyl) phosphine. The mixture was brought to 60 ° C, 44.5 mg (0.1 mmol) of bis (dibenzylideneacetone) palladium (0) was added, and the mixture was stirred at 80 ° C for 2.0 hours. After stirring, the filtrate was obtained by suction filtration through Fluorisil (Wako Pure Chemical Co., Ltd., catalog number: 540-00135), Celite (Wako Pure Chemical Industries, Ltd., catalog number: 531-16855), and alumina. The solid obtained by concentrating the obtained filtrate was purified by silica gel column chromatography (developing solvent was hexane: toluene = 1: 1) and recrystallized with a mixed solvent of toluene and hexane to give 2.8 g of a white solid in 82% yield. . The synthesis scheme of Step 1 is shown below (f-1).

<Step 2: N, N'-bis (3-methylphenyl) -N, N'-bis [3- (9-phenyl-9H-fluoren-9-yl) phenyl] pyrene-1, 6-diamine (abbreviated) Synthesis of: 1,6mMemFLPAPrn)

1, 6-dibromopyrene 0.6 g (1.7 mmol), 3-methylphenyl-3- (9-phenyl-9H-fluoren-9-yl) phenylamine 1.4 g (3.4 mmol), sodium tert-butoxide 0.5 g (5.1 mmol) was placed in a 100 mL three-necked flask and nitrogen inside the flask. To this mixture was added 21.0 mL of toluene and 0.2 mL of a 10% hexane solution of tri (tert-butyl) phosphine. The mixture was brought to 60 ° C, 34.9 mg (0.1 mmol) of bis (dibenzylideneacetone) palladium (0) was added, and the mixture was stirred at 80 ° C for 3.0 hours. After stirring, 400 mL of toluene was added to the mixture, and the mixture was heated, hot filtered, suction filtered through fluorine, celite, and alumina to obtain a filtrate. The solid obtained by concentrating the obtained filtrate was purified by silica gel column chromatography (developing solvent was hexane: toluene = 3: 2) to obtain a yellow solid. The obtained yellow solid was recrystallized with the mixed solvent of toluene and hexane, and the objective yellow solid was obtained in yield 1.2g, yield 67%.

Subsequently, 1.0 g of the obtained yellow solid was sublimed and purified by the train servation method. Sublimation purification conditions heated the yellow solid at 317 degreeC, flowing a pressure of 2.2 Pa and argon gas at a flow rate of 5.0 mL / min. After sublimation purification, 1.0 g of a yellow solid of the desired product was obtained at a yield of 93%. The synthesis scheme of Step 2 is shown in (f-2) below.

It is given in the analysis result by nuclear magnetic resonance spectroscopy ⁽¹ H-NMR) as a yellow powder obtained in the step 2. In addition, ¹ H-NMR chart is shown to FIG. 29 (A), (B). Through this result, N, N′-bis (3-methylphenyl) -N, N′-bis [3- (9-phenyl-9H-fluoren-9-yl) phenyl] pyrene-1, 6-diamine ( Abbreviated name: 1,6mMemFLPAPrn).

¹ H-NMR (CDCl ₃ , 300 MHz): δ = 2.21 (s, 6H), 6.67 (d, J = 7.2 Hz, 2H), 6.74 (d, J = 7.2 Hz, 2H), 7.17-7.23 (m, 34H), 7.62 (d, J = 7.8 Hz, 4H), 7.74 (d, J = 7.8 Hz, 2H), 7.86 (d, J = 9.0 Hz, 2H), 8.04 (d, J = 8.7 Hz, 4H) .

In Example 5, the phosphorescent organometallic iridium complex (3-ethyl-2, 4-pentanedionate) bis (4, 6-diphenylpyrimidinato) bis represented by Structural Formula (106) in Embodiment 1 (III) ) (Abbreviated as: [Ir (dppm) ₂ (eacac)]) is specifically exemplified. In addition, the structure of [Ir (dppm) ₂ (eacac)] (abbreviated) is shown below.

<Step 1; (3-ethyl-2,4-pentanedionate) bis (4,6-diphenylpyrimidinato) iridium (III) (abbreviated as: Synthesis of [Ir (dppm) ₂ (eacac)]>

First, 30 mL of 2-ethoxyethanol, 2.16 g of heteronuclear complex [Ir (dppm) ₂ Cl] ₂ , 2.00 g of 3-ethyl-2, 4-pentanedione, and 3.40 g of sodium carbonate were placed in an eggplant flask with a reflux tube. The flask was nitrogen replaced. Then, it stirred at room temperature for 48 hours, and then heated at 100 degreeC for 13 hours. The solvent was distilled off and suction filtration was performed by adding ethanol to the obtained residue. The obtained solid was washed with water followed by ethanol and recrystallized twice with a mixed solvent of dichloromethane and ethanol. The obtained solid was purified by flash column chromatography using dichloromethane as a developing solvent. Further, by recrystallization with a mixed solvent of dichloromethane and ethanol, a phosphorescent organometallic iridium complex [Ir (dppm) ₂ (eacac)] (abbreviated) was obtained as an orange powder (yield 1%). The synthesis scheme of step 1 is shown below (g-1).

In addition, the results of analysis by nuclear magnetic resonance spectroscopy ( ¹ H-NMR) of the orange powder obtained in Step 1 are shown below. As a result, in Example 5, it was found that the phosphorescent organometallic iridium complex represented by Structural Formula 106 (Ir (dppm) ₂ (eacac)) was obtained.

¹ H-NMR. δ (CDCl ₃ ): 1.04 (t, 3H), 1.95 (s, 6H), 2.27-2.30 (m, 2H), 6.46 (d, 2H), 6.79 (t, 2H), 6.89 (t, 2H), 7.56-7.62 (m, 6H), 7.78 (d, 2H), 8.18 (s, 2H), 8.24 (d, 4H), 9.18 (s, 2H).

Subsequently, analysis by ultraviolet visible absorption spectroscopy (UV) of [Ir (dppm) ₂ (eacac)] (abbreviated) was performed. The UV spectrum was measured at room temperature using an ultraviolet visible spectrophotometer (Nihon Spectrometer Co., Ltd. type V550) and using a dichloromethane solution (0.085 mmol / L). In addition, the emission spectrum of [Ir (dppm) ₂ (eacac)] (abbreviated) was measured. The emission spectrum was measured at room temperature using a fluorescence photometer (FS920 manufactured by Hamamatsu Photonics Co., Ltd.) and degassed using a dichloromethane solution (0.085 mmol / L). The measurement result is shown in FIG. The horizontal axis represents wavelength and the vertical axis represents absorption intensity and emission intensity.

As shown in Fig. 31, the phosphorescent organometallic iridium complex [Ir (dppm) ₂ (eacac)] (abbreviated) had an emission peak at 604 nm and orange emission was observed from the dichloromethane solution.

101 First electrode 102 EL layer
103 Second electrode 111 Hole injection layer
112 hole transport layer 113 light emitting layer
114 Electron Transport Layer 115 Electron Injection Layer
116 Charge Generation Layer 201 Anode
202 Cathode 203 EL Layer
204 Light Emitting Layer 205 Phosphorescent Compound
206 First Organic Compound 207 Second Organic Compound
301 First electrode 302 (1) First EL layer
302 (2) Second EL layer 304 Second electrode
305 charge generating layer (I) 401 reflective electrode
402 Transflective Semi-reflective Electrode 403a First Transparent Conductive Layer
403b 2nd transparent conductive layer 404B 1st light emitting layer (B)
404G Second Light Emitting Layer (G) 404R Third Light Emitting Layer (R)
405 EL layer 410R first light emitting device R
410G Second Light Emitting Device (G) 410B Third Light Emitting Device (B)
501 element substrate 502 pixel part
503 driving circuit section (source line driving circuit) 504 driving circuit section (gate line driving circuit)
505 Seal Material 506 Encapsulation Board
507 Wiring 508 FPC (Flexible Print Circuit)
509 n-channel TFT 510 p-channel TFT
511 Switching TFT 512 Current Control TFT
513 First electrode (anode) 514 Insulator
515 EL layer 516 Second electrode (cathode)
517 light emitting element 518 space
1100 substrate 1101 first electrode
1102 EL layer 1103 Second electrode
1111 hole injection layer 1112 hole transport layer
1113 Light Emitting Layer 1114 Electron Transport Layer
1115 Electronic Injection Layer 7100 Television Device
7101 Housing 7103 Indicator
7105 stand 7107 indicator
7109 Operation keys 7110 Remote control
7201 body 7202 housing
7203 Display 7204 Keyboard
7205 External connection port 7206 Pointing device
7301 Housing 7302 Housing
7303 Connector 7304 Indicator
7305 Display part 7306 Speaker part
7307 Recording Media Insert 7308 LED Lamp
7309 Control Key 7310 Connector
7311 Sensor 7312 Microphone
7400 mobile phone 7401 housing
7402 Display 7403 Control Button
7404 external connection port 7405 speaker
7406 Microphone 8001 Lighting
8002 Lighting 8003 Lighting
8004 Lighting 3000 Board
3001 first electrode 3002a first EL layer
3002b Second EL layer 3002c Third EL layer
3003 Second electrode 3011a First hole injection layer
3011b Second hole injection layer 3011c Third hole injection layer
3012a First hole transport layer 3012b Second hole transport layer
3012c Third hole transport layer 3013a First emission layer
3013b Second Light Emitting Layer 3013c Third Light Emitting Layer
3014a First Electron Transport Layer 3014b Second Electron Transport Layer
3014c Third electron transport layer 3015a First electron injection layer
3015b Second Electron Injection Layer 3015c Third Electron Injection Layer
3016a First Charge Generation Layer 3016b Second Charge Generation Layer

Claims (26)

A light emitting device comprising a light emitting element,
The light emitting device includes a phosphorescent organic metal iridium complex containing iridium and pyrimidine having an aryl group at position 4,
Nitrogen in the third position of the pyrimidine is coordinated to the iridium,
The pyrimidine has an alkyl group or an aryl group in any of 2nd, 5th, and 6th positions;
An ortho position of the aryl group bonded to the 4th position of the pyrimidine is bonded to the iridium.
The method of claim 1,
The phosphorescent organic metal iridium complex is represented by the following general formulas (G1), (G3), and (G5)

,

,

Appears as either
Where L represents a monoanionic ligand,
Ar represents a substituted or unsubstituted aryl group,
R ¹ to R ³ each independently represent one of hydrogen, a substituted or unsubstituted C1-C4 alkyl group, or a substituted or unsubstituted C6-C10 aryl group,
At least one of R ¹ to R ³ represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.
The method of claim 2,
The monoanionic ligand is represented by the following structural formulas (L1 to L7)

Appears as either
In formula, R <^21> -R <^58> is respectively independently hydrogen, substituted or unsubstituted C1-C4 alkyl group, halogen group, vinyl group, substituted or unsubstituted C1-C4 haloalkyl group, substituted or unsubstituted An alkoxy group having 1 to 4 carbon atoms or a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, wherein A ¹ to A ⁴ each independently represent sp ² hybrid carbon or 1 to 4 carbon atoms bonded to nitrogen or hydrogen; A light-emitting device which represents sp ² hybrid carbon bonded to any one of an alkyl group of 4, a halogen group, a haloalkyl group having 1 to 4 carbon atoms, or a phenyl group.
The method of claim 1,
The phosphorescent organic metal iridium complex has the following structural formula (100 to 102)

,

,

A light emitting device, which appears in any one of.
The method of claim 1,
And the light emitting device comprises an electroluminescent layer comprising the phosphorescent organic metal iridium complex between a pair of electrodes.
The method of claim 5, wherein
The electroluminescent layer further includes a first organic compound and a second organic compound,
And the first organic compound and the second organic compound form an exciplex.
The method of claim 1,
The light emitting device includes a plurality of electroluminescent layers between electrodes of one phase,
And at least one of the plurality of electroluminescent layers comprises the phosphorescent organic metal iridium complex.
The method of claim 1,
The light emitting device includes a first light emitting device, a second light emitting device, and a third light emitting device,
Each of the first to third light emitting devices
Reflective electrode,
A transparent conductive layer in contact with the reflective electrode,
An electroluminescent layer in contact with the transparent conductive layer and
And a semi-transmissive and semi-reflective electrode in contact with the electroluminescent layer.
The method of claim 8,
The light emitted from the first light emitting device has a longer wavelength than the light emitted from the second light emitting device, and the light emitted from the second light emitting device has a longer wavelength than the light emitted from the third light emitting device. Light emitting device.
The method of claim 1,
The light emitting device includes a first light emitting device, a second light emitting device, and a third light emitting device,
Each of the first to third light emitting devices
Reflective electrode,
A transparent conductive layer in contact with the reflective electrode,
A first electroluminescent layer in contact with the transparent conductive layer
A charge generating layer on the first electroluminescent layer,
A second electroluminescent layer over said charge generating layer, and
And a semi-transmissive semi-reflective electrode in contact with said second electroluminescent layer.
11. The method of claim 10,
The light emitted from the first light emitting device has a longer wavelength than the light emitted from the second light emitting device, and the light emitted from the second light emitting device has a longer wavelength than the light emitted from the third light emitting device. Light emitting device.
An electronic device comprising the light emitting device according to claim 1.
Lighting device comprising a light emitting device according to claim 1.
A light emitting device comprising a light emitting element,
The light emitting device includes a phosphorescent organic metal iridium complex containing iridium and 1,3,5-triazine having an aryl group on the second position,
Nitrogen in the 1st position of the 1,3,5-triazine is coordinated to the iridium,
The 1,3,5-triazine has a substituent at position 4 or 6,
An ortho position of the aryl group is bonded to the iridium.
15. The method of claim 14,
The phosphorescent organic metal iridium complex is represented by the following general formulas (G2), (G4), and (G6)

,

,

Appears as either
Where L represents a monoanionic ligand,
Ar represents a substituted or unsubstituted aryl group,
R ⁴ and R ⁵ are each independently hydrogen, a substituted or unsubstituted C 1-4 alkyl group, a substituted or unsubstituted C 1-4 alkoxy group, a substituted or unsubstituted C 1-4 alkylthio group, Any one of a halogen group, a substituted or unsubstituted haloalkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms,
At least one of R ⁴ and R ⁵ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a halogen group , A substituted or unsubstituted haloalkyl group having 1 to 4 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.
The method of claim 15,
The monoanionic ligand is represented by the following structural formulas (L1 to L7)

Appears as either
In formula, R <^21> -R <^58> is respectively independently hydrogen, substituted or unsubstituted C1-C4 alkyl group, halogen group, vinyl group, substituted or unsubstituted C1-C4 haloalkyl group, substituted or unsubstituted An alkoxy group having 1 to 4 carbon atoms or a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, wherein A ¹ to A ⁴ each independently represent sp ² hybrid carbon or 1 to 4 carbon atoms bonded to nitrogen or hydrogen; A light-emitting device which represents sp ² hybrid carbon bonded to any one of an alkyl group of 4, a halogen group, a haloalkyl group having 1 to 4 carbon atoms, or a phenyl group.
15. The method of claim 14,
The phosphorescent organic metal iridium complex has the following structural formula (103 or 104)

or

A light emitting device, which appears in any one of.
15. The method of claim 14,
And the light emitting device comprises an electroluminescent layer comprising the phosphorescent organic metal iridium complex between a pair of electrodes.
The method of claim 18,
The electroluminescent layer further includes a first organic compound and a second organic compound,
And the first organic compound and the second organic compound form an exciplex.
15. The method of claim 14,
The light emitting device includes a plurality of electroluminescent layers between electrodes of one phase,
And at least one of the plurality of electroluminescent layers comprises the phosphorescent organic metal iridium complex.
15. The method of claim 14,
The light emitting device includes a first light emitting device, a second light emitting device, and a third light emitting device,
Each of the first to third light emitting devices
Reflective electrode,
A transparent conductive layer in contact with the reflective electrode,
An electroluminescent layer in contact with the transparent conductive layer and
And a semi-transmissive semi-reflective electrode in contact with the electroluminescent layer.
22. The method of claim 21,
The light emitted from the first light emitting device has a longer wavelength than the light emitted from the second light emitting device, and the light emitted from the second light emitting device has a longer wavelength than the light emitted from the third light emitting device. Light emitting device.
15. The method of claim 14,
The light emitting device includes a first light emitting device, a second light emitting device, and a third light emitting device,
Each of the first to third light emitting devices
Reflective electrode,
A transparent conductive layer in contact with the reflective electrode,
A first electroluminescent layer in contact with the transparent conductive layer
A charge generating layer on the first electroluminescent layer,
A second electroluminescent layer over said charge generating layer, and
And a semi-transmissive semi-reflective electrode in contact with said second electroluminescent layer.
24. The method of claim 23,
The light emitted from the first light emitting device has a longer wavelength than the light emitted from the second light emitting device, and the light emitted from the second light emitting device has a longer wavelength than the light emitted from the third light emitting device. Light emitting device.
An electronic device comprising the light emitting device according to claim 14.
Lighting device comprising a light emitting device according to claim 14.

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