Aromatic amine derivative

Abstract

To provide a novel aromatic amine derivative that is favorable as an organic EL light-emitting material.SOLUTION: The invention provides a novel aromatic amine derivative represented by the general formula (G1) in the figure. (In the formula, A represents oxygen or sulfur, and R1 to R7 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group.SELECTED DRAWING: Figure 3

Description

[Technical field]

[0001] The present invention is applicable to at least a part of a light-emitting element that emits light by applying a voltage. The present invention also relates to a novel organic compound capable of producing a light-emitting element, a light-emitting device, an electronic device, and the like, which use the organic compound. The present invention relates to a lighting device and an illumination device. [Background technology]

[0002] In recent years, electroluminescence (EL) The basic structure of these light-emitting devices is as follows: is an element in which a layer containing a light-emitting substance is sandwiched between a pair of electrodes. This makes it possible to obtain light emission from the luminescent substance.

[0003] Since these light-emitting elements are self-luminous, the pixels have higher visibility than LCD displays. The advantages of this type of display include the fact that no backlight is required and that the response speed of the light-emitting element is extremely fast. For this reason, it is considered to be suitable as a flat panel display element. Another major advantage of such light-emitting devices is that they can be fabricated to be thin and lightweight.

[0004] In addition, since these light emitting elements can be formed in a film shape, surface light emission can be easily obtained. Therefore, it is possible to form a large-area element that utilizes surface light emission. This is a characteristic that is difficult to obtain with point light sources such as incandescent bulbs and LEDs, or linear light sources such as fluorescent lamps. Because it is colored, it is also highly useful as a surface light source for lighting and other applications.

[0005] The light-emitting element that utilizes electroluminescence uses an organic compound as the light-emitting substance. They can be broadly classified according to whether they are organic or inorganic compounds, but In the case of organic EL, when a voltage is applied to the light-emitting element, electrons are emitted from one of a pair of electrodes. The electrons are injected from the other side into the layer containing the light-emitting organic compound, and the .... The electrons and holes then recombine in the light-emitting organic compound, In the case of a light-emitting organic compound, an excited state is formed, and the relaxation time when returning from the excited state to the ground state is It emits light as energy.

[0006] Due to this mechanism, the above-mentioned light-emitting element is called a current-excitation type light-emitting element. The types of excited states that organic compounds can form are singlet excited states and triplet excited states. Emission from the singlet excited state is called fluorescence, and emission from the triplet excited state is called phosphorescence. is.

[0007] In addition to the excitation caused by the recombination of electrons and holes and the light emission that accompanies their relaxation, The excitation energy of the organic compound is transferred to another organic compound, Another method is to have the organic compound that emits light when it is excited and released. When the compound molecules are in high concentration, for example, stacking interactions occur, resulting in poor emission efficiency. This is an effective method when the concentration quenching occurs.

[0008] Specifically, in this method, a light-emitting material is dispersed (doped) in the light-emitting layer of an organic EL device. The organic compound molecules that emit light are doped into the host material to create stacking interactions. By suppressing the current, the efficiency of the light-emitting element can be increased. Therefore, the excitation energy is transferred from the excited host material to the dopant material, and the dopant When substance A is dispersed in a matrix made of other substance B, The substance B that constitutes the matrix is ​​called the host material, and the substance A that is dispersed in the matrix is ​​called the droplet. The organic material is called a host material (also called a guest material).

[0009] In addition, the light emitted by a luminescent material is unique to that material, and materials that emit light of good colors are In addition, it is difficult to develop a new type of IC that has other important features such as long life and low power consumption. It is extremely difficult to obtain a light-emitting element that satisfies the characteristics. This is due to the fact that it is difficult to obtain a light-emitting element that satisfies the characteristics, such as lifetime and power consumption. The important performance of optical devices does not depend only on the material that emits light, but also on the device structure and This is because the compatibility between the light-emitting material and the host material also has a large influence.

[0010] In particular, blue light-emitting elements have a shorter life span than light-emitting elements of other colors, and it is necessary to have both a long life span and good color purity. For example, in the case of a flat panel display using an organic electroluminescence (EL) display device, To commercialize flat panel displays, it is necessary to extend the life of blue light-emitting elements and improve their color purity. This is an important issue and further improvement is required. Light-emitting device materials have been proposed (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0011] [Patent Document 1] JP 2004-204238 A [Patent Document 2] International Publication No. 2005 / 108348 Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention has been made to provide a blue light-emitting device having high color purity and a long life. One aspect of the present invention is to provide a novel aromatic amine derivative having high color purity and suitable as a blue light-emitting material for organic electroluminescence (EL). One object of the present invention is to provide a conductor.

[0013] In addition, light-emitting elements, light-emitting devices, lighting devices, and One of the objects is to provide an electronic device. [Means for solving the problem]

[0014] One embodiment of the present invention is an aromatic amine derivative represented by the following general formula (G1).

[0015] [ka]

[0016] R 1 ~R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted It represents either a substituted phenyl group or a substituted or unsubstituted biphenyl group. α 1 and α 2 each independently represents a substituted or unsubstituted phenylene group. To, Ar 1 is a substituted or unsubstituted condensed aromatic hydrocarbon having 14 to 18 carbon atoms forming a ring. Furthermore, Ar 2 is a substituted or unsubstituted aryl group having 6 to 13 carbon atoms in a ring. j and n each independently represents 0 or 1, and p is 1 or 2. Furthermore, A is O (oxygen) or S (sulfur).

[0017] Another embodiment of the present invention is an aromatic amine derivative represented by the following general formula (G2).

[0018] [ka]

[0019] R 1 ~R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted It represents either a substituted phenyl group or a substituted or unsubstituted biphenyl group. α 1 and α 2 each independently represents a substituted or unsubstituted phenylene group. To, Ar 1 is a substituted or unsubstituted condensed aromatic hydrocarbon having 14 to 18 carbon atoms forming a ring. Furthermore, Ar 2 is a substituted or unsubstituted aryl group having 6 to 13 carbon atoms in a ring. j and n each independently represents 0 or 1, and p is 1 or 2. Furthermore, A is O (oxygen) or S (sulfur).

[0020] Ar in general formula (G1) and general formula (G2) 1 As the group, (Ar1-1) or (A R in the general formulas (Ar1-1) and (Ar1-2) 8 ~R 10 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, represents either a phenyl group or a substituted or unsubstituted biphenyl group, provided that the general formula (G1), and Ar in general formula (G2) 1 When the general formula (Ar1-1) is represented by the general formula (G 1), and in general formula (G2), p is 1, and general formula (G1) and general formula (G2) Ar in1 When the general formula (Ar1-2) is represented by the general formula (G1) and the general formula (G2), p is 2.

[0021] [ka]

[0022] Another embodiment of the present invention is an aromatic amine derivative represented by the following general formula (G3): General formula (G3) is a compound represented by the general formula (G1) having Ar 1 is (Ar1-2), j is 0, p is 2, It is an aromatic amine derivative.

[0023] [ka]

[0024] In general formula (G3), R 1 ~R 7 , R 8 and R 10 are each independently a hydrogen atom, a carbon atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted In addition, α represents one of the biphenyl groups. 1 represents a substituted or unsubstituted phenylene group; Also, Ar 2 represents a substituted or unsubstituted aryl group having 6 to 13 carbon atoms forming a ring. In the formula, n is 0 or 1. Furthermore, A is O (oxygen) or S (sulfur).

[0025] Another embodiment of the present invention is an aromatic amine derivative represented by the following general formula (G4): General formula (G4) is the same as general formula (G1) except that 1 is (Ar1-2), j is 1, and p is 2. It is an aromatic amine derivative.

[0026] [ka]

[0027] In general formula (G4), R 1 ~R 7 , R 8 and R 10 are each independently a hydrogen atom, a carbon atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted In addition, α represents one of the biphenyl groups. 1 and α 2 are each independently a substitution or Represents an unsubstituted phenylene group. 2 The ring is a substituted or unsubstituted ring having 6 to 13 carbon atoms. or an unsubstituted aryl group. n is 0 or 1. A is O (oxygen) or is S (sulfur).

[0028] In general formulae (G1) to (G4), α 1 ~α 2 are each independently represented by the following structural formula: It is preferable that it is any one of (α-1) to (α-3).

[0029] [ka]

[0030] Another embodiment of the present invention is an aromatic amine derivative represented by the following general formula (G5): General formula (G5) is a compound represented by the general formula (G4), 2 Aromatic amine derivatives having the structural formula (α-2) It is.

[0031] [ka]

[0032] In general formula (G5), R1 ~R 7 , R 8 and R 10 are each independently a hydrogen atom, a carbon atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted In addition, α represents one of the biphenyl groups. 1 represents a substituted or unsubstituted phenylene group; Also, Ar 2 represents a substituted or unsubstituted aryl group having 6 to 13 carbon atoms forming a ring. In the formula, n is 0 or 1. Furthermore, A is O (oxygen) or S (sulfur).

[0033] In general formula (G5), n is 0 or 1, similarly to general formulas (G1) to (G4), When n is 1, α 1 is any one of the structural formulas (α-1) to (α-3) shown above. It is preferable.

[0034] In the general formulae (G1) to (G5), Ar 2 are represented by the following structural formulas (Ar2-1) to (A It is preferable that the formula is any one of the formulas represented by r2-6).

[0035] [ka]

[0036] In general formulae (G1) to (G5), R 1 ~R 10 are each independently represented by the following structural formula: It is preferably any one of (R-1) to (R-9).

[0037] [ka]

[0038] Another embodiment of the present invention is an aromatic amine derivative represented by the following general formula (G6).

[0039] [ka]

[0040] In general formula (G6), A is O (oxygen) or S (sulfur).

[0041] Another embodiment of the present invention is an aromatic amine derivative represented by the following general formula (G7).

[0042] [ka]

[0043] In the general formula (G7), A is O (oxygen) or S (sulfur).

[0044] Another embodiment of the present invention is an aromatic amine derivative represented by the following general formula (G8).

[0045] [ka]

[0046] In general formula (G8), A is O (oxygen) or S (sulfur).

[0047] Another embodiment of the present invention is a light-emitting element having an EL layer between a pair of electrodes, The light-emitting layer includes an aromatic amine derivative (general formula (G1) to general formula (G8) )) is characterized in that it includes any one of the following:

[0048] Further, one embodiment of the present invention is a light-emitting device formed using the above-described light-emitting element, and a light-emitting element comprising the light-emitting element. The present invention relates to an electronic device formed using the light-emitting device. be.

[0049] Further, one embodiment of a light-emitting device of the present invention includes the above-described light-emitting element and a control means for controlling light emission of the light-emitting element. In this specification, the light-emitting device includes an image display device, a light-emitting device, Also, the panel includes a connector, such as an FPC (Flexible printed circuit) or TAB (Tape A utomated bonding tape or TCP (Tape Carrier) Modules with attached TAB tape or TCP printed on them A module with a wiring board or a light-emitting element with COG (Chip On Glass) ) method, all modules in which ICs (integrated circuits) are directly mounted are also included in the light-emitting device. do. Effect of the Invention

[0050] The aromatic amine derivative according to one embodiment of the present invention is capable of emitting visible light with a short wavelength and has high color purity. Good blue light emission can be obtained.

[0051] In addition, by using the aromatic amine derivative of one embodiment of the present invention, the light-emitting efficiency and reliability A light-emitting element with high light emission efficiency can be obtained.

[0052] Furthermore, by using this light-emitting element, highly reliable light-emitting devices, electronic devices, and lighting devices can be manufactured. A bright device can be obtained. [Brief description of the drawings]

[0053] [Figure 1] 1A and 1B are diagrams illustrating light-emitting elements. [Diagram 2] 1A and 1B are diagrams illustrating light-emitting elements. [Diagram 3] 1A and 1B are diagrams illustrating light-emitting elements. [Figure 4] 1A and 1B are diagrams illustrating a light-emitting device. [Diagram 5] 1A and 1B are diagrams illustrating a light-emitting device. [Figure 6] 1A to 1C are diagrams illustrating electronic devices. [Figure 7] 1A and 1B are diagrams illustrating a lighting device. [Figure 8] A diagram showing the 1H NMR chart of FrA-II. [Figure 9] A diagram showing the 1H NMR chart of 1,6FrAPrn-II. [Figure 10] FIG. 1 shows the absorption spectrum and emission spectrum of 1,6FrAPrn-II in a toluene solution. [Figure 11] FIG. 1 shows the absorption and emission spectra of a thin film of 1,6FrAPrn-II. [Figure 12] A diagram showing the 1H NMR chart of ThA-II. [Figure 13] A diagram showing the 1H NMR chart of 1,6ThAPrn-II. [Figure 14] FIG. 1 shows the absorption spectrum and emission spectrum of 1,6ThAPrn-II in a toluene solution. [Figure 15] FIG. 1 shows the absorption and emission spectra of a thin film of 1,6ThAPrn-II. [Figure 16] A diagram showing the 1H NMR chart of 1,6FrAPrn. [Figure 17] FIG. 1 shows the absorption spectrum and emission spectrum of 1,6FrAPrn in a toluene solution. [Figure 18] FIG. 1 shows the absorption and emission spectra of a thin film of 1,6FrAPrn. [Figure 19] A diagram showing the 1H NMR chart of 1,6ThAPrn. [Figure 20] FIG. 1 shows the absorption spectrum and emission spectrum of 1,6ThAPrn in a toluene solution. [Figure 21] FIG. 1 shows the absorption and emission spectra of a thin film of 1,6ThAPrn. [Figure 22] A diagram showing the 1H NMR chart of 1,6mFrBAPrn-II. [Figure 23] FIG. 1 shows the absorption spectrum and emission spectrum of 1,6mFrBAPrn-II in a toluene solution. [Figure 24] FIG. 1 shows the absorption and emission spectra of a thin film of 1,6mFrBAPrn-II. [Diagram 25] A diagram showing the 1H NMR chart of 1,6mThBAPrn-II. [Figure 26] FIG. 1 shows the absorption spectrum and emission spectrum of 1,6mThBAPrn-II in a toluene solution. [Figure 27] FIG. 1 shows the absorption and emission spectra of a thin film of 1,6mThBAPrn-II. [Figure 28] FIG. 1H NMR chart of 1,6FrBAPrn-II. [Figure 29] FIG. 1 shows the absorption spectrum and emission spectrum of 1,6FrBAPrn-II in a toluene solution. [Diagram 30] FIG. 1 shows the absorption and emission spectra of a thin film of 1,6FrBAPrn-II. [Diagram 31] 1A to 1C are diagrams illustrating light-emitting elements according to an embodiment of the present invention. [Diagram 32] 13 shows characteristics of Light-emitting Elements 1 to 4. [Diagram 33] 13 shows characteristics of Light-emitting Elements 1 to 4. [Diagram 34] 13 shows characteristics of Light-emitting Elements 1 to 4. [Diagram 35] 13 shows characteristics of Light-emitting Elements 1 to 4. [Diagram 36] 13 is a graph showing characteristics of light-emitting elements 5 to 7. [Figure 37] 13 is a graph showing characteristics of light-emitting elements 5 to 7. [Figure 38] 13 is a graph showing characteristics of light-emitting elements 5 to 7. [Figure 39] 13 is a graph showing characteristics of light-emitting elements 5 to 7. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0054] Hereinafter, the embodiment of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the above description, and the embodiments and aspects of the present invention may be modified without departing from the spirit and scope of the present invention. It will be readily understood by those skilled in the art that various modifications may be made to the embodiments and details of the present invention. The present invention is not to be construed as being limited to the description of the embodiments shown below.

[0055] (Embodiment 1) In this embodiment, an aromatic amine derivative which is one embodiment of the present invention will be described.

[0056] The aromatic amine derivative of the present embodiment is represented by the following general formula (G1) and the following general formula (G2). The aromatic amine derivative is represented by the following formula:

[0057] [ka]

[0058] [ka]

[0059] R 1 ~R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted It represents either a substituted phenyl group or a substituted or unsubstituted biphenyl group. α 1 or α 2 each independently represents a substituted or unsubstituted phenylene group. To, Ar 1 is a substituted or unsubstituted condensed aromatic hydrocarbon having 14 to 18 carbon atoms forming a ring. Furthermore, Ar2 is a substituted or unsubstituted aryl group having 6 to 13 carbon atoms in a ring. Each of j and n is independently 0 or 1, and p is 1 or 2. Furthermore, A is O (oxygen) or S (sulfur).

[0060] In addition, the substituent R in the general formula (G1) and the general formula (G2) 1 ~R 7 Using an alkyl group as In the case where the compound is used, the solubility in an organic solvent is improved, so that purification becomes easy, which is preferable. By improving the uniformity of the film formed, the uniformity of the film is improved when organic EL elements are produced by the wet method. This is preferable.

[0061] In addition, the molecule contains a dibenzofuranyl group or a dibenzothiophenyl group, which is a bulky and three-dimensional structure. Because of its high structure, interactions between molecules are suppressed, and the morphology (molecular shape) This improves the film quality and suppresses concentration quenching and excimer formation. It becomes easier.

[0062] Furthermore, the dibenzofuranyl group and the dibenzothiophenyl group are electrochemically stable. For this reason, dibenzofuran is contained in the molecules represented by the general formula (G1) and the general formula (G2). Compounds with phenyl and dibenzothiophenyl groups are highly efficient and have a long life. It can be said that it is suitable as a light-emitting material.

[0063] Ar in general formula (G1) and general formula (G2) 1 is represented by the following general formula (Ar1-1) or ( In the general formulas (Ar1-1) and (Ar1-2), R 8 ~R 1 0each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, represents either a phenyl group or a substituted or unsubstituted biphenyl group; Ar 1 is the general formula In the case of (Ar1-1), p in the general formula (G1) and the general formula (G2) is 1, and In the case of Ar1-2), p is 2.

[0064] [ka]

[0065] The compound has a substituent represented by the general formula (Ar1-1) and a substituent represented by the general formula (Ar1-2) in the molecule. The aromatic amine derivatives represented by the general formula (G1) and the general formula (G2) have excellent quantum yields and luminescence efficiencies. This is preferable because it increases the rate.

[0066] The substituents R in the general formulae (Ar1-1) and (Ar1-2) 8 ~R 10 As Al Even if the compound has an alkyl group, it has improved solubility in organic solvents, making it easier to purify. This is also preferable when producing an organic EL device, since it improves the uniformity of the film formed. The molecules form a more three-dimensional structure, improving the film quality and suppressing concentration quenching and excimer formation. It becomes easier to control.

[0067] In addition, R 1 ~R 7 , α 1 and α 2 , Ar 2 When each of the groups has a substituent, the substituent Examples of the alkyl group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a pentyl group, and a hexyl group. and aryl groups such as phenyl and biphenyl groups. The し characters may be linked together to form a ring.

[0068] As a means for solving the above problems, a compound represented by the following general formula (G3) is prepared by the method of the present invention. ) of the compound represented by the formula 1 In the general formula (Ar1-2), j is 0 and p is 2. It is preferred to use the R 1 ~R 7 , R 8 and R 10 are independent of each other a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, or Represents either a substituted or unsubstituted biphenyl group. 1 is a substituted or unsubstituted phenanthroline. Represents an ylene group. Ar 2 is a substituted or unsubstituted aryl group having 6 to 13 carbon atoms forming a ring. represents a aryl group, n is 0 or 1, and A is O (oxygen) or S (sulfur).

[0069] [ka]

[0070] In order to solve the above problems, the present invention provides a compound represented by the following general formula (G9): The compound represented by Ar 1 Aromatic amine derivatives where j is 0 and p is 2, are (Ar1-2) The body may be used. 1 ~R 7 , R 8 and R 10 are each independently a hydrogen atom, a carbon atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted represents one of the biphenyl groups. 1 represents a substituted or unsubstituted phenylene group. r 2 represents a substituted or unsubstituted aryl group having 6 to 13 carbon atoms forming a ring. is 0 or 1, and A is O (oxygen) or S (sulfur).

[0071] [ka]

[0072] Furthermore, in the compound represented by the general formula (G1), the compound represented by the following general formula (G4) To, Ar 1 Aromatic amine derivatives in which R is (Ar1-2), j is 1, and p is 2 are also preferred. 1 ~R 7 , R 8 and R 10 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. , a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group. It represents either. 1 and α 2 each independently represents a substituted or unsubstituted phenylene group. Ar 2 represents a substituted or unsubstituted aryl group having 6 to 13 carbon atoms forming a ring. n is 0 or 1, and A is O (oxygen) or S (sulfur).

[0073] [ka]

[0074] The aromatic amine derivatives represented by the general formulas (G3), (G4) and (G9) are The half-width of the emission spectrum is narrow, and it is easy to obtain an emission color with high color purity. It is easy to obtain blue light emission. In addition, the Stokes shift is small, so this material can be used in organic electroluminescence devices. When doped as a light-emitting material, energy transfer from the host material occurs efficiently, High luminous efficiency is easily achieved.

[0075] Furthermore, the general formula (G1) can be used as a general formula (G3), a general formula (G4) and a general formula (G9). ) or by changing p in the general formula (G2) to 2, the molecular weight increases and the thermal properties improve. Therefore, when used as a light-emitting material in an organic EL device, the deposition stability is improved.

[0076] In the general formulae (G1) to (G4) and (G9), α 1 ~α 2 Yes, that Each of them is preferably independently any one of the following structural formulas (α-1) to (α-3): It is.

[0077] [ka]

[0078] Furthermore, as shown in the following general formula (G5), α in the above general formula (G4) 2 The above structural formula (α -2) makes the molecular structure bulkier and suppresses interactions between molecules, resulting in improved thermal properties. It can be a good structure. 1 ~R 7 , R 8 and R 10 are each independently a nitrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, or or an unsubstituted biphenyl group. 1 represents a substituted or unsubstituted phenylene Represents the Ar group. 2 represents a substituted or unsubstituted aryl group having 6 to 13 carbon atoms forming a ring. In the formula, n is 0 or 1, and A is O (oxygen) or S (sulfur).

[0079] [ka]

[0080] In general formula (G5), n is 0 or 1, similarly to general formulas (G1) to (G4), When n is 1, α 1 is any one of the structural formulas (α-1) to (α-3) shown above. It is preferable.

[0081] In the above general formulae (G1) to (G5) and (G9), Ar 2 Below It is preferably any one of the structural formulae (Ar2-1) to (Ar2-6).

[0082] [ka]

[0083] In addition, in the above-mentioned general formulae (G1) to (G5) and general formula (G9), R 1 ~R 10 are each independently any one of the following structural formulas (R-1) to (R-9): It is preferable that there is.

[0084] [ka]

[0085] Aromatic amine derivatives represented by general formulae (G1) to (G5) and general formula (G9) Specific examples of the compound include aromatic amine derivatives represented by structural formulas (100) to (380). However, the present invention is not limited to these.

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[0156] As a method for synthesizing the aromatic amine derivative of the present embodiment, various reactions can be applied. For example, the present invention represented by the general formula (G1) can be obtained by carrying out the synthesis method shown below. The aromatic amine derivative according to the embodiment of the present invention can be synthesized. The method for synthesizing the aromatic amine derivative is not limited to the following synthesis method.

[0157] <Method for synthesizing aromatic amine derivative represented by general formula (G1)> As shown in the synthesis scheme (A-1), a dibenzofuran derivative or a dibenzothiophene derivative A halogenated aryl compound (a1) having an amine (a2) is coupled with a halogenated aryl compound (a1) having an amine (a2). By coupling, the amine derivative (a3) ​​can be obtained.

[0158] [ka]

[0159] In the synthesis scheme (A-1), A represents O (oxygen) or S (sulfur), and R 1 ~R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted represents a substituted phenyl group, or a substituted or unsubstituted biphenyl group. α 1 and α 2 each independently represents a substituted or unsubstituted phenylene group. r 2 j, n represent a substituted or unsubstituted aryl group having 6 to 13 carbon atoms forming a ring. are each independently 0 or 1. 1 represents a halogen, and is highly reactive. Of these, bromine or iodine is preferred, and iodine is more preferred.

[0160] In the synthesis scheme (A-1), a dibenzofuran derivative or a dibenzothiophene derivative Conductive halides and aryl compounds with amines (primary arylamine compounds, There are various reaction conditions for the coupling reaction with arylamines (e.g., secondary arylamine compounds). As an example, a synthesis method using a metal catalyst in the presence of a base can be applied.

[0161] In the synthesis scheme (A-1), when the Hartwig-Buchwald reaction is used, As the metal catalyst, a palladium catalyst can be used. A mixture of palladium complexes and their ligands can be used. Specific palladium complexes Examples include bis(dibenzylideneacetone)palladium(0) and palladium(II) acetate. etc.

[0162] The ligands include tri(tert-butyl)phosphine and tri(n-hexyl)phosphine. phenylphosphine, tricyclohexylphosphine, 1,1-bis(diphenylphosphino)phenanthroline, Examples include Rosene (abbreviation: DPPF).

[0163] Substances that can be used as bases include sodium tert-butoxide and other organic solvents. Examples of the base include organic bases and inorganic bases such as potassium carbonate.

[0164] This reaction is preferably carried out in a solution, and examples of the solvent that can be used include toluene, xylene, benzene, etc. However, the catalysts and their ligands that can be used The solvents, bases, and bases are not limited to these. In addition, this reaction is carried out under inert gas such as nitrogen or argon. It is preferable to carry out the reaction in a hydrophilic atmosphere.

[0165] In addition, in the synthesis scheme (A-1), the case where the Ullmann reaction is used is shown. A copper catalyst can be used as the catalyst. Specifically, copper iodide (I) or copper acetate ( II). In addition, examples of substances that can be used as bases include potassium carbonate. and the like inorganic bases.

[0166] This reaction is preferably carried out in a solution. Solvents that can be used include 1,3-dichlorophenyl Methyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU), Toluene However, the catalyst, base, solvent, etc. that can be used are The solvent is not limited to these. This reaction is carried out under an inert atmosphere such as nitrogen or argon. It is preferable to carry out the process in the following manner.

[0167] In the Ullmann reaction, the reaction temperature of 100°C or higher can produce the desired product in a shorter time and in a higher yield. Therefore, it is preferable to use a solvent with a high boiling point such as DMPU or xylene. The reaction temperature is preferably 150°C or higher, so that DM having a higher boiling point is used. It is more preferable to use PU as the solvent.

[0168] Next, as shown in the synthesis scheme (A-2), the amine derivative (a3) ​​and the halogenated array By coupling with amine (a4), an aromatic amine derivative represented by general formula (G1) can be obtained. You can get a body.

[0169] [ka]

[0170] In the synthesis scheme (A-2), A represents O (oxygen) or S (sulfur), and R 1 ~R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted represents a substituted phenyl group, or a substituted or unsubstituted biphenyl group. α 1 and α 2 each independently represents a substituted or unsubstituted phenylene group. r 1 represents a substituted or unsubstituted condensed aromatic hydrocarbon having 14 to 18 carbon atoms forming a ring. Also, Ar 2 represents a substituted or unsubstituted aryl group having 6 to 13 carbon atoms forming a ring. j and n each independently represent 0 or 1, and p represents 1 or 2. 2 represents a halogen, and is preferably bromine or iodine due to its high reactivity, and more preferably is iodine.

[0171] In this case, when p=1, the amine derivative (a3) ​​is reacted with the halogenated arene (a4) When p=2, the amine derivative (a3) ​​is reacted with the halogenated arene (a4) in an equivalent amount. and react 2 equivalents.

[0172] In the synthesis scheme (A-2), an aryl compound having a halogen group and an amine with aryl compounds (primary arylamine compounds or secondary arylamine compounds) There are various reaction conditions for the coupling reaction. One example is a metal catalyst in the presence of a base. In the synthesis scheme (A-2), As in the synthesis scheme (A-1), the Hartwig-Buchwald reaction and the Ullmann reaction are used. That's good.

[0173] In this manner, the aromatic amine derivative (G1) of the present embodiment can be synthesized. .

[0174] <Method for synthesizing aromatic amine derivative represented by general formula (G2)> First, as shown in the synthesis scheme (A-3), a dibenzofuran derivative or a dibenzothio The halogenated olefin derivative (a5) and the aryl compound (a6) having an amine are reacted with each other to form a compound having an aryl group. By coupling, the amine derivative (a7) is obtained.

[0175] [ka]

[0176] In the synthesis scheme (A-3), A represents O (oxygen) or S (sulfur), and R 1 ~R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted represents a substituted phenyl group, or a substituted or unsubstituted biphenyl group. α 1 and α 2 each independently represents a substituted or unsubstituted phenylene group. r 2 j, n represent a substituted or unsubstituted aryl group having 6 to 13 carbon atoms forming a ring. are each independently 0 or 1. 1 represents a halogen, and is highly reactive. Of these, bromine or iodine is preferred, and iodine is more preferred.

[0177] In the synthesis scheme (A-3), a dibenzofuran derivative or a dibenzothiophene derivative Conductive halides and aryl compounds with amines (primary arylamine compounds, There are various reaction conditions for the coupling reaction with arylamines (or secondary arylamine compounds). As an example, a synthesis method using a metal catalyst in the presence of a base can be applied.

[0178] In the synthetic scheme (A-3), when the Hartwig-Buchwald reaction is used, As the metal catalyst, a palladium catalyst can be used. A mixture of palladium complexes and their ligands can be used. Specific palladium complexes Examples include bis(dibenzylideneacetone)palladium(0) and palladium(II) acetate. etc.

[0179] The ligands include tri(tert-butyl)phosphine and tri(n-hexyl)phosphine. , tricyclohexylphosphine, and 1,1-bis(diphenylphosphino)ferro Sen (abbreviation: DPPF), etc.

[0180] Substances that can be used as bases include sodium tert-butoxide and other organic solvents. Examples of suitable bases include organic bases and inorganic bases such as potassium carbonate. This reaction is carried out in a solution. It is preferable that the solvent used is toluene, xylene, benzene, etc. However, the catalysts and their ligands, bases, and solvents that can be used are not limited to these. This reaction should be carried out under an inert atmosphere such as nitrogen or argon. is preferred.

[0181] In addition, the synthesis scheme (A-3) shows the case where the Ullmann reaction is used. A copper catalyst can be used as the catalyst. Specifically, copper iodide (I) or copper acetate ( II). In addition, examples of substances that can be used as bases include potassium carbonate. and the like inorganic bases.

[0182] In addition, this reaction is preferably carried out in a solution, and examples of the solvent that can be used include 1, 3-Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU) , toluene, xylene, benzene, etc. However, the catalysts and salts that can be used The groups and solvents are not limited to those mentioned above. This reaction is carried out in an inert atmosphere such as nitrogen or argon. It is preferable to carry out the reaction under atmosphere.

[0183] In the Ullmann reaction, the reaction temperature of 100°C or higher can produce the desired product in a shorter time and in a higher yield. Therefore, it is preferable to use a solvent with a high boiling point such as DMPU or xylene. The reaction temperature is preferably 150°C or higher, so that DM having a higher boiling point is used. It is more preferable to use PU as the solvent.

[0184] Next, as shown in the synthesis scheme (A-4), the amine derivative (a7) and the halogenated array were reacted to form a By coupling with amine (a8), an aromatic amine derivative represented by general formula (G2) can be obtained. You can get a body.

[0185] [ka]

[0186] In the synthesis scheme (A-4), A represents O (oxygen) or S (sulfur), and R 1 ~R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted represents a substituted phenyl group, or a substituted or unsubstituted biphenyl group. α 1 and α 2 each independently represents a substituted or unsubstituted phenylene group. r 1 represents a substituted or unsubstituted condensed aromatic hydrocarbon having 14 to 18 carbon atoms forming a ring. Also, Ar 2 represents a substituted or unsubstituted aryl group having 6 to 13 carbon atoms forming a ring. j and n each independently represent 0 or 1, and p represents 1 or 2. 3 represents a halogen, and is preferably bromine or iodine due to its high reactivity, and more preferably is iodine.

[0187] In this case, when p=1, the amine derivative (a7) is reacted with the halogenated arene (a8) When p=2, the amine derivative (a7) is reacted with the halogenated arene (a8). and react 2 equivalents.

[0188] In the synthesis scheme (A-4), an aryl compound having a halogen group and an amine The aryl compounds (primary arylamine compounds or secondary arylamine compounds) There are various reaction conditions for the coupling reaction. One example is a reaction using a metal catalyst in the presence of a base. The synthesis methods used can be applied.

[0189] In the synthesis scheme (A-4), similarly to the synthesis scheme (A-3), The Buchwald reaction and the Ullmann reaction can be used.

[0190] In this manner, the aromatic amine derivative (G2) of the present embodiment can be synthesized. .

[0191] The aromatic amine derivative (G1) or the aromatic amine derivative (G2) of the present embodiment has a short Amine derivatives capable of emitting visible light of wavelengths and producing blue light with good color purity. It is a body.

[0192] In addition, the aromatic amine derivative (G1) or the aromatic amine derivative (G2) of the present embodiment By forming a light-emitting element using this, the characteristics of the light-emitting element can be improved.

[0193] Note that this embodiment mode can be freely combined with other embodiment modes.

[0194] (Embodiment 2) In this embodiment, the aromatic compound represented by the general formula (G3) or (G9) shown in the first embodiment is Aromatic amine derivatives and aromatic amines represented by general formula (G6) and general formula (G10) The derivatives will be described.

[0195] The following general formula (G6) represents a compound represented by general formula (G3),1 ~R 7 , R 8 oh YobiR 10 is a hydrogen atom, and Ar 2 is the structural formula (Ar2-1) shown in embodiment 1. and n is 0 and A is O (oxygen) or S (sulfur). The aromatic amine derivative represented by the following general formula (G6) is characterized in that The dibenzofuranyl or dibenzothiophenyl group forms a tertiary amine at its 4-position. That is the thing.

[0196] [ka]

[0197] In addition, the following general formula (G10) represents a compound represented by general formula (G9), 1 ~R 7 , R 8 and R 10 is a hydrogen atom, and Ar 2 The structural formula (Ar2- 1) where n is 0 and A is O (oxygen) or S (sulfur). The aromatic amine derivative in the following general formula (G10) is characterized by the following general formula: The dibenzofuranyl or dibenzothiophenyl group in (G9) forms a tertiary amine at its 2-position. This is what has been achieved.

[0198] [ka]

[0199] The aromatic amine derivatives represented by the general formula (G6) and the general formula (G10) both have high luminescence efficiency. It is a luminescent material with high efficiency and long life, but it has four dibenzofuranyl or dibenzothiophenyl groups. The aromatic amine derivative represented by the general formula (G6), which forms a tertiary amine at the The general formula for forming a tertiary amine at the 2-position of a dibenzofuranyl or dibenzothiophenyl group (G10) is preferred because it produces a blue color with good color purity. This is because dibenzofuranyl or dibenzothiophenyl groups form tertiary amines. This is because the conjugation of the light-emitting material molecules differs depending on the bonding position of the light-emitting material. This is because the difference in the conjugation of the material molecules shifts the peak position of the emission spectrum to the shorter wavelength side. be.

[0200] In addition, in the aromatic amine derivative represented by the general formula (G6) or the general formula (G10), A is O (oxygen) rather than S (sulfur) for the dibenzothiophenyl group. The furanyl group has a peak in the emission spectrum that appears on the shorter wavelength side, which leads to better color purity. It turns a deep blue color.

[0201] That is, an aromatic amine derivative represented by the general formula (G6) or an aromatic amine derivative represented by the general formula (G10) Among the aromatic amine derivatives that can be used, A is O (oxygen) and the 4-position of the dibenzofuranyl group is The compound with structural formula (G6-1), which forms a tertiary amine, exhibits the most pure blue color. do.

[0202] [ka]

[0203] <Method for synthesizing aromatic amine derivative represented by general formula (G6)> A method for synthesizing a blue-colored compound having high efficiency, long life, and high color purity represented by general formula (G6) As an example, the synthesis scheme (A-5) is shown below. can be obtained.

[0204] [ka]

[0205] As shown in the synthetic scheme (A-5), the secondary aromatic amine derivative (a9) and the halogenated pyridine derivative (b1) are By coupling with arylene (a10), an aromatic amine represented by general formula (G6) In the synthesis scheme (A-5), A can be O (oxygen) or or S (sulfur). X 2 represents a halogen, preferably bromine or the like, due to its high reactivity. or iodine, more preferably iodine.

[0206] In the synthesis scheme (A-5), a pyrene compound having a halogen group and a pyrene compound having an amine Catalysis with aryl compounds (primary arylamine compounds or secondary arylamine compounds) There are various reaction conditions for the coupling reaction. As in the first embodiment, a metal catalyst is used in the presence of a base. The Hartwig-Buchwald reaction and the Ullmann reaction are used to synthesize In this case, the amine derivative (a9) is reacted with the halogenated pyrene (a10) in a ratio of 2: By reacting in equivalent amounts, the compound of general formula (G6) can be synthesized.

[0207] <Method for synthesizing secondary aromatic amine derivative (a9) represented by general formula (G11)> Here, the synthesis method of the secondary aromatic amine derivative (a9) shown in the synthesis scheme (A-5) will be described. The following will be explained using general formula (G11). As an example, It is possible.

[0208] [ka]

[0209] In the synthesis scheme (A-6), A represents O (oxygen) or S (sulfur), and R 1 ~R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted represents a substituted phenyl group, or a substituted or unsubstituted biphenyl group. α 1 represents a substituted or unsubstituted phenylene group. 2 is the number of carbon atoms forming the ring It represents a substituted or unsubstituted aryl group having an amino acid sequence of 6 to 13. n is 0 or 1. The X may be any of those described in the first embodiment. 1 represents a halogen and is reactive In view of the high molecular weight distribution, bromine or iodine is preferred, and iodine is more preferred.

[0210] The reaction shown in the synthesis scheme (A-6) is carried out by using a dibenzofuran derivative or a dibenzothiophene derivative. Halides of phenyl derivatives and aryl compounds with amines (primary arylamine compounds) This coupling reaction is carried out with a secondary arylamine compound. The reaction can be carried out under various reaction conditions. The Hartwig-Buchwald reaction and Ullmann reaction are carried out using metal catalysts in the presence of base. The above synthesis method can be applied.

[0211] As shown in the synthesis scheme (A-5), blue light with high efficiency, long life, and high color purity is obtained. In order to obtain an aromatic amine derivative represented by the general formula (G6) which exhibits a color of 1) is required. Furthermore, a secondary aromatic amine derivative represented by the general formula (G11) is required. The secondary aromatic amine derivatives are novel substances and very useful compounds.

[0212] [ka]

[0213] As described above, by using the compound shown in this embodiment, the organic EL device which is the subject of the present invention can be obtained. It is possible to provide a novel aromatic amine derivative which is suitable as a blue light emitting material for use in a liquid crystal display device. By forming a light-emitting element using the novel aromatic amine derivative described in this embodiment mode, This makes it possible to improve the characteristics of the light emitting device.

[0214] Note that this embodiment mode can be freely combined with other embodiment modes.

[0215] (Embodiment 3) In this embodiment, an aromatic amine derivative represented by general formula (G4) shown in Embodiment 1 is In particular, α in general formula (G4) will be described. 2 The general formula is the above structural formula (α-2). In (G5), R 1 ~R 7 , R 8 and R 10 is a hydrogen atom, and Ar 2 The above structure General formula (G7) in which n is 0 and is represented by formula (Ar2-1) will be described. In formula (G4), α 2 is (α-1), and R 1 ~R 7 , R 8 and R 10 is a hydrogen atom Yes, Ar 2 is the above structural formula (Ar2-1), and is represented by general formula (G8) in which n is 0. The aromatic amine derivatives that can be used are also described.

[0216] [ka]

[0217] [ka]

[0218] The general formula (G7) is characterized in that the dibenzofuranyl group or the dibenzothiophenyl group is The phenylene group is bonded to the amino group at the meta position. The characteristic of 8) is that a dibenzofuranyl group or a dibenzothiophenyl group is bonded to an amino group. The phenylene group is bonded at the para position. A in formula (G8) is O (oxygen) or S (sulfur).

[0219] The aromatic amine derivatives represented by the general formula (G7) and the general formula (G8) are both highly efficient. It is a long-life luminescent material, but the dibenzofuranyl group or dibenzothiophenyl group is The aromatic amine derivative represented by the general formula (G7) bonded at the meta position of the diphenyl group is A benzofuranyl or dibenzothiophenyl group is attached at the para position of the phenylene group. The emission spectrum is shifted to the shorter wavelength side compared to the aromatic amine derivative represented by general formula (G8). Therefore, it is possible to produce a blue color with higher color purity.

[0220] <Method for synthesizing aromatic amine derivative represented by general formula (G7)> As a synthesis method for the compound represented by the general formula (G7), various reactions can be applied. For example, it can be obtained by the synthesis scheme (A-7).

[0221] [ka]

[0222] The reaction shown in the synthetic scheme (A-7) is carried out by converting a halogen group into Pyrene compounds having an amine group and aryl compounds having an amine group (primary arylamine compounds, or secondary arylamine compounds). The reaction can be carried out under various reaction conditions. Synthesis using metal catalysts in the presence of base, such as the Wigg-Buchwald reaction and the Ullmann reaction The method can be applied.

[0223] As shown in the synthetic scheme (A-7), a secondary aromatic amine derivative (a13) and a halogenated By coupling with pyrene (a10), the amine derivative represented by the general formula (G7) can be obtained. In this case, the secondary aromatic amine derivative (a13) is reacted with a halogenated pyridine to obtain the product. By reacting two equivalents of the compound (a10), the compound of general formula (G7) can be synthesized. In addition, this reaction is preferably carried out in a solution, and examples of the solvent that can be used include the following: The solvents described in the first embodiment can be used. In addition, the reaction can be carried out under nitrogen, argon, or other gases. It is preferable to carry out the reaction under an inert atmosphere such as X. 2 represents a halogen, and due to its high reactivity, Bromine or iodine is preferable, and iodine is more preferable. 7), A represents O (oxygen) or S (sulfur).

[0224] (Embodiment 4) In this embodiment, a photoresist is formed using the aromatic amine derivative described in any of the embodiments 1 to 3. The optical element will now be described.

[0225] The light-emitting element in this embodiment has a first electrode functioning as an anode and a second electrode functioning as a cathode. A second electrode and an EL layer provided between the first electrode and the second electrode. In the light-emitting element in this embodiment, the first electrode has a higher potential than the second electrode. It is assumed that light emission is obtained when a voltage is applied to each of them so that

[0226] In addition, the EL layer of the light-emitting element in this embodiment is formed by stacking the first electrode functioning as an anode and the second electrode functioning as an anode. The first layer (hole injection layer), the second layer (hole transport layer), the third layer (light emitting layer), the fourth layer (electrode The layer comprises a first layer (electron transport layer) and a fifth layer (electron injection layer).

[0227] The structure of the light-emitting element in this embodiment will be described with reference to FIG. The substrate 101 is made of, for example, glass, quartz, or plastic. A flexible substrate may be used. A flexible substrate is a material that can be easily attached to a substrate. For example, polycarbonate, poly Examples of the substrate include plastic substrates made of arylate and polyethersulfone. Film (polypropylene, polyester, vinyl, polyvinyl fluoride, polyvinyl chloride, etc.) An inorganic vapor deposition film may also be used.

[0228] The substrate 101 is a light emitting device or a product that uses the light emitting element of this embodiment. may remain in the electronic device, but it should not remain in the final product and should be removed during the manufacturing process of the light-emitting element. It may have only a function as a support.

[0229] The first electrode 102 formed on the substrate 101 is made of a material having a large work function (specifically, 4.0 It is preferable to use metals, alloys, electrically conductive compounds, and mixtures thereof. Specifically, for example, indium oxide-tin oxide (ITO) n Oxide), indium oxide-tin oxide containing silicon or silicon oxide, indium oxide Indium zinc oxide (IZO), tungsten oxide In addition, gold (Au), white (Pb), and indium oxide containing zinc oxide are also included. Gold (Pt), Nickel (Ni), Tungsten (W), Chromium (Cr), Molybdenum (M o), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), titanium (Ti ), or nitrides of metal materials (for example, titanium nitride). In this embodiment, the first layer 11 of the EL layer 103 formed in contact with the first electrode 102 1 is a composite material that is easy to inject holes into regardless of the work function of the first electrode 102. Since it is formed using Compounds and mixtures thereof, as well as other elements belonging to Groups 1 and 2 of the Periodic Table Any known material can be used as long as it is a material having a high thermal conductivity (including a low thermal conductivity material).

[0230] These materials can be formed by sputtering. For example, indium oxide Indium-zinc oxide (IZO) is a type of indium oxide that is made by adding 1 to 10 wt% zinc oxide. The target is indium oxide containing tungsten oxide and zinc oxide. It contains 0.5 to 5 wt% tungsten oxide and 0.1 to 1 wt% zinc oxide relative to the amount of zinc. By using such a target, it can be formed by a sputtering method. It may be formed by a vacuum deposition method, a coating method, an ink jet method, a spin coating method, or the like.

[0231] In addition, in the EL layer 103 formed on the first electrode 102, When a layer containing a composite material described later is used as the material for the first layer 111 to be formed, In the first electrode 102, various metals and alloys can be used regardless of the magnitude of the work function. , electrically conductive compounds, and mixtures thereof. For example, aluminum Aluminum (Al), silver (Ag), and alloys containing aluminum (AlSi) can also be used. Cut.

[0232] In addition, materials with small work functions are elements belonging to Groups 1 and 2 of the periodic table, i.e. Alkali metals such as lithium (Li) and cesium (Cs), and magnesium (Mg ), calcium (Ca), strontium (Sr), and other alkaline earth metals, Alloys containing (MgAg, AlLi), europium (Eu), ytterbium (Yb), etc. It is also possible to use rare earth metals such as those mentioned above and alloys containing these.

[0233] The first electrode 1 may be made of an alkali metal, an alkaline earth metal, or an alloy containing these metals. When forming the layer 02, a vacuum deposition method or a sputtering method can be used. When using silver paste, a coating method or an inkjet method can be used. do.

[0234] The EL layer 103 formed on the first electrode 102 is made of the aromatic fluorine-containing compound shown in any one of the first to third embodiments. In addition to amine derivatives, known materials can be used, including low molecular weight compounds and high molecular weight compounds. The EL layer 103 can be formed from any of organic compounds. This includes not only those consisting of inorganic compounds alone, but also those containing inorganic compounds as part of the composition.

[0235] The EL layer 103 is, for example, a hole injection layer including a substance with a high hole injection property and a hole transport layer including a substance with a high hole transport property. A hole transport layer including a material having a high electron transporting property, a light emitting layer including a material having a high electron transporting property, By appropriately combining and laminating a transport layer and an electron injection layer containing a material with high electron injection properties, is formed.

[0236] In addition, the EL layer 103 shown in FIG. 1A is a layer including a first layer (a hole injection layer) from the first electrode 102 side. ) 111, a second layer (hole transport layer) 112, a third layer (light emitting layer) 113, a fourth layer (electron A fifth layer (electron transport layer) 114 and a fifth layer (electron injection layer) 115 are laminated in this order.

[0237] The first layer 111 is a hole-injection layer containing a substance with high hole-injection properties. The oxides are molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, and ruthenium oxide. tantalum oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide In addition, the following can be used: Low molecular weight organic compounds include phthalocyanine (abbreviation: HPc), copper(II) phthalocyanine, Examples include phthalocyanine compounds such as anthraquinone (abbreviation: CuPc).

[0238] In addition, the low molecular weight organic compound 4,4',4''-tris(N,N-diphenylamino) ) Triphenylamine (abbreviation: TDATA), 4,4',4''-tris[N-(3-methylphenyl) (N-phenylamino)triphenylamine (abbreviation: MTDATA), 4 ,4'-Bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl DPAB, 4,4'-bis(N-{4-[N'-(3-methylphenyl)- N'-phenylamino]phenyl}-N-phenylamino)biphenyl (abbreviation: DNTP D) 1,3,5-tris[N-(4-diphenylaminophenyl)-N-phenylamine N-(9-phenylcarbazol-3-yl)benzene (abbreviation: DPA3B) )-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA1), 3, 6-Bis[N-(9-phenylcarbazol-3-yl)-N-phenylamino]-9- Phenylcarbazole (abbreviation: PCzPCA2), 3-[N-(1-naphthyl)-N-( 9-phenylcarbazol-3-yl)amino]-9-phenylcarbazole (abbreviation: P CzPCN1) and other aromatic amine compounds. Aromatic amine derivatives can also be used.

[0239] Furthermore, polymeric compounds (oligomers, dendrimers, polymers, etc.) can also be used. For example, poly(N-vinylcarbazole) (abbreviation: PVK), poly(4-vinyltrifluoroethylene) phenylamine) (abbreviation: PVTPA), poly[N-(4-{N'-[4-(4-diphenyl phenyl-N'-phenylamino}phenyl)methacrylamide (abbreviation: PTPDMA), poly[N,N'-bis(4-butylphenyl)-N,N'-bi Examples of polymer compounds include poly(phenyl)benzidine (abbreviation: Poly-TPD). In addition, poly(3,4-ethylenedioxythiophene) / poly(styrenesulfonic acid) (PEDOT / PSS), polyaniline / poly(styrenesulfonic acid) (PAni / PS It is also possible to use a polymer compound to which an acid such as S) has been added.

[0240] In addition, the first layer 111 may be formed by adding an acceptor substance to a substance having a high hole transporting property. A composite material can be used. Note that a material with high hole transport properties can be used that contains an acceptor material. By using a material having such a structure, it is possible to select a material for forming the electrode regardless of the work function of the electrode. In other words, not only a material with a large work function but also a material with a low work function can be used for the first electrode 102. These composite materials can be made of a material with high hole transport properties and an arsenic compound. The film can be formed by co-evaporating the acceptor material. In this regard, composite does not simply mean mixing two materials, but mixing multiple materials. This means that a state is created in which charge can be exchanged between materials.

[0241] The organic compounds used in the composite materials include aromatic amine compounds, carbazole derivatives, aromatic Various compounds such as aromatic hydrocarbons and polymer compounds (oligomers, dendrimers, polymers, etc.) As the organic compound used for the composite material, a compound having a high hole transporting property can be used. It is preferable that the organic compound is a compound having a low molecular weight. -6 cm 2 Hole transfer above / Vs However, it is preferable that the material has a higher hole transporting property than the electron transporting property. Other organic compounds that can be used in the composite material are listed below. List things specifically.

[0242] Examples of organic compounds that can be used in composite materials include MTDATA and TDATA. , DPAB, DNTPD, DPA3B, PCzPCA1, PCzPCA2, PCzPCN 1,4,4'-Bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB), N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1' -biphenyl]-4,4'-diamine (abbreviation: TPD), 4-phenyl-4'-(9-phenyl Aromatic alkylamines such as (phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP) amine compounds, 4,4'-di(N-carbazolyl)biphenyl (abbreviation: CBP), 1,3 ,5-Tris[4-(N-carbazolyl)phenyl]benzene (abbreviation: TCPB), 9- [4-(N-carbazolyl)phenyl]-10-phenylanthracene (abbreviation: CzPA ), 9-phenyl-3-[4-(10-phenyl-9-anthryl)phenyl]-9H- Carbazole (abbreviation: PCzPA), 1,4-bis[4-(N-carbazolyl)phenyl ]-2,3,5,6-tetraphenylbenzene and other carbazole derivatives. Cut.

[0243] In addition, 2-tert-butyl-9,10-di(2-naphthyl)anthracene (abbreviation: t- BuDNA), 2-tert-butyl-9,10-di(1-naphthyl)anthracene, 9 ,10-Bis(3,5-diphenylphenyl)anthracene (abbreviation: DPPA), 2-t ert-Butyl-9,10-bis(4-phenylphenyl)anthracene (abbreviation: tB uDBA), 9,10-di(2-naphthyl)anthracene (abbreviation: DNA), 9,10- Diphenylanthracene (abbreviation: DPAnth), 2-tert-butylanthracene ( Abbreviation: t-BuAnth), 9,10-bis(4-methyl-1-naphthyl)anthracene (abbreviation: DMNA), 9,10-bis[2-(1-naphthyl)phenyl]-2-tert -Butylanthracene, 9,10-bis[2-(1-naphthyl)phenyl]anthracene , 2,3,6,7-tetramethyl-9,10-di(1-naphthyl)anthracene, etc. Examples of suitable aromatic hydrocarbon compounds include aromatic hydrocarbon compounds.

[0244] Furthermore, 2,3,6,7-tetramethyl-9,10-di(2-naphthyl)anthracene, 9,9'-bianthryl, 10,10'-diphenyl-9,9'-bianthryl, 10, 10'-Bis(2-phenylphenyl)-9,9'-bianthryl, 10,10'-bis [(2,3,4,5,6-pentaphenyl)phenyl]-9,9'-bianthryl, an Thracene, tetracene, rubrene, perylene, 2,5,8,11-tetra(tert-bu Aromatic hydrocarbon compounds such as 4,4'-bis( 2,2-diphenylvinyl)biphenyl (abbreviation: DPVBi), 9,10-bis[4-( 2,2-diphenylvinyl)phenyl]anthracene (abbreviation: DPVPA) and other vinyl groups Also, an aromatic hydrocarbon compound having the following structure can be mentioned. The aromatic amine derivatives shown can also be used.

[0245] In addition, 7,7,8,8-tetramethylphenylacetate is an acceptor material that can be used in composite materials. tetracyano-2,3,5,6-tetrafluoroquinodimethane (abbreviation: F4-TCNQ), Examples of the organic compounds include chloranil and transition metal oxides. Examples of the oxides of metals belonging to groups 4 to 8 in the above-mentioned formula are oxides of metals belonging to groups 4 to 8 in the above-mentioned formula. Vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide Rhenium oxide, manganese oxide, and rhenium oxide are preferred because of their high electron-accepting properties. Molybdenum chloride is preferred because it is stable in the air, has low hygroscopicity, and is easy to handle.

[0246] In addition, the above-mentioned polymer compounds such as PVK, PVTPA, PTPDMA, and Poly-TPD The above-mentioned acceptor substance may be used to form a composite material for the first layer 111. Furthermore, the aromatic amine derivatives shown in the first to third embodiments can be used in combination with the above-mentioned acceptor. Alternatively, the first layer 111 may be formed from a composite material by combining the polymer with a polymerizable substance.

[0247] The second layer 112 is a layer containing a substance having a high hole-transporting property. For example, 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB) and N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[ 1,1'-biphenyl]-4,4'-diamine (abbreviation: TPD), 4-phenyl-4'- (9-Phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP), 4 ,4'-Bis[N-(9,9-dimethylfluoren-2-yl)-N-phenylamino] Biphenyl (abbreviation: DFLDPBi), 4,4',4''-tris(N,N-diphenyl amino)triphenylamine (abbreviation: TDATA), 4,4',4''-tris[N-( 3-Methylphenyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA ), 4,4'-bis[N-(spiro-9,9'-bifluoren-2-yl)-N-phenyl Aromatic amine compounds such as bis(amino)biphenyl (abbreviation: BSPB) can be used. The substances mentioned here are mainly -6 cm 2 / Vs or more. However, other materials may be used as long as they have a higher hole transporting property than electron transporting property. In addition, the aromatic amine derivatives shown in the first to third embodiments can also be used. The layer containing a substance having a high hole transporting property is not limited to a single layer, and may be a layer containing the above substance. The layer may be a laminate of two or more layers.

[0248] The second layer 112 may also contain a carbazole derivative such as CBP, CzPA, or PCzPA. Alternatively, anthracene derivatives such as t-BuDNA, DNA, and DPAnth may be used. .

[0249] The second layer 112 is made of poly(N-vinylcarbazole) (abbreviation: PVK) or poly (4-vinyltriphenylamine) (abbreviation: PVTPA) and other polymer compounds. It is also possible.

[0250] The third layer 113 is a light-emitting layer containing a highly light-emitting substance. The composition is mainly composed of luminous substances, or highly luminous substances are dispersed in other substances. In this embodiment mode, the highly light-emitting substance shown in any one of the embodiments 1 to 3 is used. An aromatic amine derivative is used.

[0251] When the aromatic amine derivatives shown in the first to third embodiments are dispersed in other substances, The proportion of the aromatic amine derivatives shown in the forms 1 to 3 in the above is 10% or less by mass. In addition, as a material for dispersing the luminescent material, a known material may be used. However, a luminescent substance (the aromatic amine derivative shown in any of the embodiments 1 to 3) can be used. ) has a shallower (smaller absolute value) lowest unoccupied molecular orbital level (LUMO level) than the highest occupied molecular orbital level It is preferable to use a substance having a deep HOMO level (large absolute value).

[0252] Specifically, tris(8-quinolinolato)aluminum(III) (abbreviation: Alq), Tris(4-methyl-8-quinolinolato)aluminum(III) (abbreviation: Almq3), Bis(10-hydroxybenzo[h]quinolinato)beryllium(II) (abbreviation: BeBq 2) Bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum (III) (abbreviation: BAlq), bis(8-quinolinolato)zinc(II) (abbreviation: Znq ), bis[2-(2-benzoxazolyl)phenolato]zinc(II) (abbreviation: ZnPB O), bis[2-(2-benzothiazolyl)phenolato]zinc(II) (abbreviation: ZnBT Z) can be used.

[0253] Also, 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4 -Oxadiazole (abbreviation: PBD), 1,3-bis[5-(p-tert-butylphenyl) 1,3,4-oxadiazol-2-yl]benzene (abbreviation: OXD-7), 3 -(Biphenyl-4-yl)-4-phenyl-5-(4-tert-butylphenyl)- 1,2,4-Triazole (abbreviation: TAZ), 2,2',2''-(1,3,5-benzene (1-phenyl-1H-benzimidazole) (abbreviation: TPBI), Bathophenanthroline (abbreviated as BPhen), bathocuproine (abbreviated as BCP), etc. Heterocyclic compounds can be used.

[0254] Others include 9-[4-(N-carbazolyl)phenyl]-10-phenylanthracene (abbreviation Name: CzPA), 9-[4-(3,6-diphenyl-N-carbazolyl)phenyl]-1 0-Phenylanthracene (abbreviation: DPCzPA), 9,10-bis(3,5-diphenyl 9,10-di(2-naphthyl)anthracene (abbreviation: DPPA), DNA, 2-tert-butyl-9,10-di(2-naphthyl)anthracene Sen (abbreviation: t-BuDNA), 9,9'-Bianthryl (abbreviation: BANT), 9,9' -(Stilbene-3,3'-diyl)diphenanthrene (abbreviation: DPNS), 9,9'- (Stilbene-4,4'-diyl)diphenanthrene (abbreviation: DPNS2), 3,3', Condensation of 3''-(benzene-1,3,5-triyl)tripylene (abbreviation: TPB3) Aromatic compounds may also be used.

[0255] In addition, multiple types of materials can be used to disperse the light-emitting material. In order to suppress the crystallization, a substance such as rubrene that suppresses the crystallization may be further added. In order to transfer energy to the light substance more efficiently, NPB or Alq, etc., is added. In this way, by using a structure in which a light-emitting material is dispersed in another material, the third layer 1 In addition, the high concentration of highly luminescent materials can suppress the crystallization of 13. This can suppress concentration quenching.

[0256] In addition, a light-emitting substance may be dispersed in the above-mentioned substance, particularly in the electron transporting substance, to form the third layer. It is more preferable to form 113. Specifically, the above-mentioned metal complexes, heterocyclic compounds, Among the condensed aromatic compounds, CzPA, DNA, t-BuDNA, and the The polymer compounds listed as the materials that can be used for the layer 114 in the fourth embodiment can also be used. Cut.

[0257] The third layer 113 may be formed of two or more layers. When the third layer 113 is formed by laminating the first light-emitting layer and the second light-emitting layer in this order from the hole transport layer side, A substance having hole transport properties is used as the host material of the first light-emitting layer, and a substance having hole transport properties is used as the host material of the second light-emitting layer. A substance having an electron transporting property can be used as the host of the first light-emitting layer. The material used is one that has a higher hole transporting property than an electron transporting property, and the host material of the second emitting layer is a hole A material having a higher electron transporting property than a transporting property is preferable. The space between the first and second light-emitting layers becomes the light-emitting region, resulting in a more efficient element.

[0258] When the third layer 113 described above is made of a plurality of materials, the materials are deposited by co-evaporation using a vacuum deposition method. Vapor deposition, or a method using a mixed solution, such as an inkjet method, a spin coating method, or It can be prepared by using a dip coating method or the like.

[0259] The fourth layer 114 is an electron transport layer containing a substance with a high electron transport property. For example, low molecular weight organic compounds include Alq, Almq3, BeBq2, BAlq, and Z Metal complexes such as nq, ZnPBO, and ZnBTZ can be used. In addition, heterocyclization such as PBD, OXD-7, TAZ, TPBI, BPhen, and BCP The substances mentioned here are mainly 10 -6 cm 2 / Vs or more electrons In addition, if a material has a higher electron transporting property than a hole transporting property, Other materials may be used as the electron transport layer. The electron transport layer may be a single layer or a multilayer. Alternatively, two or more layers made of the above-mentioned substances may be laminated.

[0260] Moreover, a polymer compound can also be used for the fourth layer 114. For example, poly[(9, 9-Dihexylfluorene-2,7-diyl)-co-(pyridine-3,5-diyl)] (abbreviation: PF-Py), poly[(9,9-dioctylfluorene-2,7-diyl)-c o-(2,2'-bipyridine-6,6'-diyl)] (abbreviation: PF-BPy) It is possible.

[0261] The fifth layer 115 is an electron injection layer containing a substance with high electron injection properties. 5 includes lithium fluoride (LiF), cesium fluoride (CsF), and calcium fluoride (C aF2) and the like, alkali metals, alkaline earth metals, or compounds thereof can be used. In addition, substances having electron transport properties include alkali metals, alkaline earth metals, and The compound containing these compounds, specifically, magnesium (Mg) in Alq In this case, the electron injection from the second electrode 104 may be performed. It can be done more efficiently.

[0262] The second electrode 104 is made of a metal, an alloy, or an electrode having a small work function (specifically, 3.8 eV or less). It is preferable to use an electrically conductive compound and a mixture thereof. Examples of materials include elements in groups 1 and 2 of the periodic table, such as lithium. Alkali metals such as Li and Cs, as well as magnesium, calcium, Alkaline earth metals such as Ca, Sr, and alloys containing these metals ( Rare earth metals such as MgAg, AlLi), europium (Eu), and ytterbium (Yb) and alloys containing these.

[0263] The second electrode 104 is formed using an alkali metal, an alkaline earth metal, or an alloy containing these. When forming the insulating layer, a vacuum deposition method or a sputtering method can be used. When a printing plate or the like is used, a coating method, an ink-jet method, or the like can be used.

[0264] By providing the fifth layer 115, the Al, Ag, I Various conductive materials such as indium oxide-tin oxide containing TO, silicon or silicon oxide are available. The second electrode 104 can be formed using these conductive materials. The film can be formed by a coating method, an ink jet method, a spin coating method, or the like.

[0265] In addition, the first layer (hole injection layer) 111, the second layer (hole transport layer) 112, and the third layer (light emitting layer) layer) 113, a fourth layer (electron transport layer) 114, and a fifth layer (electron injection layer) 115 are arranged in this order. The EL layer 103 to be formed by subsequent lamination may be produced by any of a variety of methods, including dry and wet methods. For example, a vacuum deposition method, an inkjet method, or a spin coating method can be used. It is also possible to use a different formation method for each layer.

[0266] The second electrode 104 may be formed by a dry method such as sputtering or vacuum deposition. It can be formed by a wet method using a paste of a metal material.

[0267] The first electrode 102, the first layer (hole injection layer) 111, and the second layer (hole transport layer) The gap between the first layer (light emitting layer) 112 and the third layer (light emitting layer) 113 is mainly for holes to flow. In order to reduce the injection barrier, the HOMO levels (work functions in the case of metals) are the same or comparable. Similarly, the third layer (light emitting layer) 113 and the fourth layer (electron transport layer) Between the first layer (electron injection layer) 114, the fifth layer (electron injection layer) 115, and the second electrode 104, a layer is formed mainly for passing electrons. In order to reduce the carrier injection barrier between adjacent layers, the LUMO level (working state in the case of metals) is It is desirable that the difference between the two functions be the same or comparable. It is preferable that the difference be within 0.2 eV, and more preferably It is preferably within 0.1 eV.

[0268] In addition, the H between the second layer (hole transport layer) 112 and the third layer (light emitting layer) 113 The OMO level, the LUMO level between the third layer (light-emitting layer) 113 and the fourth layer (electron transport layer) 114 By increasing the potential difference, carriers can be trapped in the light-emitting layer, resulting in a more efficient light-emitting element. However, in this case, if the barrier is too large, the driving voltage becomes high, which increases the burden on the element. Therefore, the difference is preferably within 0.4 eV, more preferably within 0.2 eV. It is preferable.

[0269] In the light emitting element of this embodiment, a potential difference generated between the first electrode 102 and the second electrode 104 Current flows due to this, and holes and electrons are recombined in the EL layer 103 to produce light-emitting The organic compound forms an excited state, and the relaxation energy when returning from the excited state to the ground state is This light emission is transmitted to either the first electrode 102 or the second electrode 104. Thus, the electric current is taken out through either the first electrode 102 or the second electrode 103. Either one or both of the electrodes 104 must be an electrode having light transmitting properties.

[0270] In addition, in the case where only the first electrode 102 is a light-transmitting electrode, as shown in FIG. As shown in FIG. 1, the light emitted from the EL layer 103 passes through the first electrode 102 and is extracted from the substrate 101 side. In addition, when only the second electrode 104 is a light-transmitting electrode, As shown in the figure, light emitted from the EL layer 103 is emitted from the opposite side of the substrate 101 through the second electrode 104. Furthermore, both the first electrode 102 and the second electrode 104 are transparent. In the case of an electrode having the above structure, as shown in FIG. 2(C), light emitted from the EL layer 103 is 102 and the second electrode 104, taken from both.

[0271] The structure of the layers provided between the first electrode 102 and the second electrode 104 is the same as that described above. At least the second layer 112 which is a hole transport layer and the first layer 113 which is a light emitting layer are not limited to the above. As long as it has three layers 113, other configurations than those described above may be used.

[0272] As shown in FIG. 1B, a second electrode 104 functioning as a cathode is provided on the substrate 101. The EL layer 103 and the first electrode 102 functioning as an anode may be laminated in this order. In this case, the EL layer 103 is formed by forming a fifth layer 115 on the second electrode 104 and a fourth layer 116 on the second electrode 104. 14, a third layer 113, a second layer 112, a first layer 111, and a first electrode 102 are laminated in this order. The result is a structure.

[0273] By using the light-emitting element of this embodiment mode, a passive matrix light-emitting device or a thin Active matrix type in which the driving of light-emitting elements is controlled by thin film transistors (TFTs) A light emitting device can be manufactured.

[0274] In the case of manufacturing an active matrix type light emitting device, the structure of the TFT is particularly For example, a staggered or inverted staggered TFT may be used as appropriate. The driving circuit formed on the TFT substrate is also composed of N-type and P-type TFTs. Alternatively, the TFT may be composed of only one of N-type TFT or P-type TFT. Furthermore, there is no particular limitation on the crystallinity of the semiconductor film used in the TFT. An amorphous semiconductor film or a crystalline semiconductor film may be used.

[0275] As described above, the light-emitting element shown in this embodiment uses the aromatic compound of any one of the embodiments 1 to 3 as a light-emitting substance. Since the light-emitting element is formed by containing an aromatic amine derivative, the element efficiency is improved and the light-emitting element has a long life. It can be said that:

[0276] (Embodiment 5) In this embodiment, a light-emitting element (hereinafter referred to as an EL layer) having a structure in which a plurality of light-emitting units (hereinafter referred to as an EL layer) are stacked is The embodiment of the light-emitting device (hereinafter referred to as a stacked type device) will be described with reference to FIG. The light emitting device is a stacked light emitting device having a plurality of light emitting units between a first electrode and a second electrode. The configuration of each light-emitting unit may be the same as that shown in the fourth embodiment. That is, the light-emitting element shown in the embodiment 4 is a light-emitting element having one light-emitting unit. In this embodiment mode, a light-emitting element having a plurality of light-emitting units will be described.

[0277] In FIG. 3A, a first light-emitting unit is disposed between a first electrode 321 and a second electrode 322. A first electrode 321 and a second light-emitting unit 312 are laminated. The pole 322 can be the one described in the fourth embodiment. The first light-emitting unit 311 and the second light-emitting unit 312 may have the same structure or different structures. In addition, the configuration can be the same as that of the fourth embodiment.

[0278] When a voltage is applied between the first electrode 321 and the second electrode 322, the charge generating layer 313 generates a A layer that injects electrons into the light-emitting unit on one side and holes into the light-emitting unit on the other side. In other words, it is a structure that includes an organic compound with high hole transport properties and an electron acceptor. Even if the composition contains an organic compound with high electron transport properties and an electron donor (donor), The laminated structure may be a single layer or a laminated structure of multiple layers. It is preferable that the layer for injecting holes and the layer for injecting electrons are laminated.

[0279] The hole injection layer is made of molybdenum oxide, vanadium oxide, rhenium oxide, or ruthenium oxide. Alternatively, a semiconductor or insulator such as ZnO can be used as a material having a high hole transporting property. A structure in which an acceptor substance is added may be used. The layer containing the acceptor material contains 7,7,8,8-tetracyano-2 ,3,5,6-Tetrafluoroquinodimethane (abbreviation: F4-TCNQ) and vanadium oxide These include metal oxides such as tungsten oxide, molybdenum oxide, and tungsten oxide. Examples of compounds include aromatic amine compounds, carbazole derivatives, aromatic hydrocarbons, polymer compounds, and olefins. Various compounds such as oligomers, dendrimers, and polymers can be used. The aromatic amine derivatives of the present invention shown in the first to third embodiments can also be used in the same manner. In addition, a material with a high hole transporting property is one having a hole mobility of 10 -6 cm 2 / Vs or more However, it is preferable to use a material that has a higher hole transporting property than an electron transporting property. Other materials may be used, for example. Composite materials containing these materials have excellent carrier injection and carrier transport properties, making them suitable for low-voltage operation and low-current operation. The drive can be realized.

[0280] The electron injection layer can be made of insulators such as lithium oxide, lithium fluoride, and cesium carbonate. A semiconductor can be used. Alternatively, a donor substance can be added to a substance with high electron transport properties. The donor substance may be an alkali metal or an alkaline earth metal. Group 13 metals or rare earth metals or metals belonging to Group 13 of the Periodic Table and their oxides; Carbonates can be used. Specifically, lithium (Li), cesium (Cs), magnesium Nesium (Mg), Calcium (Ca), Ytterbium (Yb), Indium (In) It is preferable to use tetrathiazol-1, lithium oxide, cesium carbonate, etc. As a material having high electron transport properties, an organic compound such as tetrahydrofuran may be used. The materials described in any of Embodiments 1 to 3 can be used for the electron transport layer. As a highly conductive material, the electron mobility is 10 -6 cm 2 / Vs or more. However, other materials that have a higher electron transporting property than holes may be used. A composite material having a substance with high electron transport properties and a donor substance may be used. It has excellent charge injection and carrier transport properties, making it possible to achieve low-voltage and low-current operation. do.

[0281] For the charge generation layer 313, the electrode material shown in Embodiment Mode 4 can also be used. For example, a layer containing a material with high hole transport properties, a metal oxide, and a transparent conductive film are combined. From the viewpoint of light extraction efficiency, the charge generating layer is preferably a layer having high light transmittance. preferable.

[0282] In any case, the charge between the first light-emitting unit 311 and the second light-emitting unit 312 When a voltage is applied between the first electrode 321 and the second electrode 322, the generating layer 313 generates a If electrons are injected into the light-emitting unit on one side and holes are injected into the light-emitting unit on the other side, For example, the voltage is set so that the potential of the first electrode is higher than the potential of the second electrode. When an electric field is applied, the charge generating layer 313 injects electrons into the first light-emitting unit 311 and the second light-emitting unit 312 emits light. Any configuration that injects holes into the light-emitting unit 312 may be used.

[0283] In this embodiment, a light emitting element having two light emitting units has been described. ) the same applies to a light-emitting element having three or more stacked light-emitting units. As in the light-emitting element according to the present embodiment, a plurality of light-emitting elements are formed between a pair of electrodes. By separating the units with charge generating layers, high brightness areas can be achieved while keeping the current density low. Since the current density can be kept low, a long-life element can be realized. In the case of lighting applications, the voltage drop due to the resistance of the electrode material can be reduced, making it possible to It is also possible to realize a light-emitting device that can be driven at a low voltage and consumes low power. It is possible.

[0284] In addition, by making the emission color of each light-emitting unit different, For example, a light-emitting element having two light-emitting units can be In this case, the luminous color of the first light-emitting unit and the luminous color of the second light-emitting unit are in a complementary color relationship. By doing so, it is possible to obtain a light emitting element that emits white light as a whole. In addition, complementary colors are colors that become achromatic when mixed together. By mixing the light from materials that emit different colors, white light can be obtained. The same applies to the case of a light-emitting element having three light-emitting units. For example, the first light-emitting unit The emission color of the first light-emitting unit is red, the emission color of the second light-emitting unit is green, and the emission color of the third light-emitting unit is red. When the emitted light color of the first is blue, the light emitting element as a whole can emit white light.

[0285] Note that this embodiment mode can be appropriately combined with other embodiment modes.

[0286] (Embodiment 6) In this embodiment, a light emitting device having the light emitting element of embodiment 4 or embodiment 5 in a pixel portion is The light emitting device will be described with reference to FIG. 4. FIG. 4(A) is a top view showing the light emitting device, and FIG. FIG. 4B is a cross-sectional view taken along lines A-A' and B-B' in FIG. 4A.

[0287] In FIG. 4A, 401 indicated by a dotted line is a driving circuit section (a source side driving circuit), 402 is The reference numeral 404 denotes a sealing substrate, and the reference numeral 403 denotes a driving circuit section (gate side driving circuit). 405 is a sealant, and the inside surrounded by the sealant 405 is void as shown in FIG. 4(B). The interval is 407.

[0288] The lead wiring 408 is connected to the source side driver circuit 401 and the gate side driver circuit 403. This is the wiring for transmitting the input signal, and is the external input terminal FPC (flexible printed circuit board). Print circuit) 409 to receive video signal, clock signal, start signal, reset signal Although only the FPC is shown here, the FPC also has a printer. A printed wiring board (PWB) may be attached. This includes not only the light emitting device itself, but also the state in which the FPC or PWB is attached to it. This shall be done.

[0289] Next, the cross-sectional structure will be described with reference to FIG. In this embodiment, the source side driving circuit 40 which is a driving circuit section is formed. 1 and one pixel in the pixel section 402. The source side driver circuit 401 is A CMOS circuit is formed by combining a channel type TFT423 and a P-channel type TFT424. The driving circuit is made up of various CMOS circuits, PMOS circuits, or NMOS circuits. In this embodiment, a driver integrated type in which a driver circuit is formed on a substrate is shown. However, this is not necessarily required, and the drive circuit can be formed externally instead of on the substrate. .

[0290] The pixel section 402 includes a switching TFT 411, a current control TFT 412 and its driver. The pixel is formed of a plurality of pixels including a first electrode 413 electrically connected to the drain. An insulator 414 is formed to cover the end portion of the first electrode 413 .

[0291] The insulator 414 may be a negative type that becomes insoluble in an etchant when irradiated with light, or a photo-irradiated type that becomes insoluble in an etchant when irradiated with light. A positive photosensitive material that becomes soluble in an etchant upon irradiation with radiation can be used. In order to improve the covering property, the upper end or the lower end of the insulator 414 is formed with a curved surface. For example, the material of the insulator 414 is a positive photosensitive acrylic resin. By using a rill, the insulator 414 has a radius of curvature (0.2 μm to 3 μm) only at the top end. It is possible to give the shape a curved surface.

[0292] An EL layer 416 and a second electrode 417 are formed on the first electrode 413. Here, the material used for the first electrode 413 may be various metals, alloys, electrically conductive materials, etc. Compounds and mixtures thereof can be used. The materials shown as usable for the first electrode in the fourth embodiment can be used. It is possible.

[0293] The EL layer 416 is formed by deposition using a deposition mask, inkjet printing, or spin coating. The EL layer 416 is formed by the method described in the fourth embodiment or the fifth embodiment. The EL layer 416 has the structure shown in FIG. 1. In addition, other materials constituting the EL layer 416 include low molecular weight The compound may be a polymer compound (including an oligomer and a dendrimer). Materials used for the EL layer may be not only organic compounds but also inorganic compounds.

[0294] The second electrode 417 may be made of various metals, alloys, and electrically conductive compounds. The second electrode 417 is used as a cathode. In particular, metals, alloys, and electrical It is preferable to use conductive compounds and mixtures thereof. For example, Elements belonging to the first or second group of the Alkali metals, as well as magnesium (Mg), calcium (Ca), and strontium (S Alkaline earth metals such as Al, Ag, and AlLi, etc. can be.

[0295] In addition, in the case where the light generated in the EL layer 416 is transmitted through the second electrode 417, The electrode 417 is made of a thin metal film and a transparent conductive film (indium oxide-silicon oxide). Indium tin oxide (ITO), indium oxide-tin oxide containing silicon or silicon oxide, indium oxide Indium-zinc oxide (IZO), tungsten oxide, and zinc oxide-containing indium oxide It is also possible to use a laminate with a material such as a rubber.

[0296] Furthermore, the sealing substrate 404 is bonded to the element substrate 410 with a sealant 405, A space 407 surrounded by an element substrate 410, a sealing substrate 404, and a sealant 405 contains light-emitting elements. The space 407 is filled with a filler. In addition to being filled with an inert gas (nitrogen, argon, etc.), it is also possible to fill it with a sealant 405. In some cases.

[0297] It is preferable to use an epoxy resin for the sealing material 405. It is preferable that the material is as impermeable to moisture and oxygen as possible. The materials used include glass and quartz substrates, as well as FRP (Fiberglass-Reinforced Plastics). forced plastics), PVF (polyvinyl fluoride), polyester Alternatively, a plastic substrate made of acrylic or the like can be used.

[0298] As described above, the active element having the light-emitting element described in the fourth or fifth embodiment is A positive matrix light emitting device can be obtained.

[0299] In addition, the light-emitting device described in the fourth or fifth embodiment may be formed by using the above-mentioned active matrix. The present invention can be used not only in a low-cost type light-emitting device but also in a passive matrix type light-emitting device. FIG. 5 is a perspective view of a passive matrix light-emitting device using the light-emitting element shown in the above embodiment. 5A is a perspective view showing a light emitting device, and FIG. 5B is a cross-sectional view showing the light emitting device. FIG. 2 is a cross-sectional view taken along XY in FIG.

[0300] In FIG. 5, an EL layer 502 is disposed between a first electrode 502 and a second electrode 503 on a substrate 501. 04 is provided. The end of the first electrode 502 is covered with an insulating layer 505. And A partition layer 506 is provided on the insulating layer 505. The side walls of the partition layer 506 are in contact with the substrate surface. As the side walls get closer to each other, the distance between the side walls becomes narrower. That is, the cross section of the partition layer 506 in the short side direction is trapezoidal, and the base (insulating layer 506 in FIG. 5B) is The side in contact with the insulating layer 505) is shorter than the upper side (the side not in contact with the insulating layer 505 in FIG. 5(B)). In this way, by providing the partition layer 506, the defect of the light-emitting element caused by static electricity or the like can be prevented. It can prevent good things.

[0301] As described above, a passive matrix light-emitting device having the light-emitting element according to the fourth or fifth embodiment can be obtained. can be obtained.

[0302] Note that the light-emitting device (active matrix type, passive matrix type ) are formed using the light-emitting element having high light-emitting efficiency and long life shown in the above embodiment mode. As a result, power consumption is reduced, and a highly reliable light emitting device can be obtained.

[0303] Note that this embodiment mode can be used in appropriate combination with the structures shown in other embodiment modes. It is decided that.

[0304] (Embodiment 7) In this embodiment, an electronic device and a lighting device each including the light-emitting device shown in Embodiment 6 are The following describes the device. The electronic devices include cameras such as video cameras and digital cameras, Goggle-type displays, navigation systems, audio playback devices (car audio, audio Audio components, computers, game devices, mobile information terminals (mobile computers , mobile phones, portable game machines, electronic books, etc.), image playback devices equipped with recording media (specific In particular, it can play recording media such as Digital Versatile Disc (DVD). These electronic devices include a display device that can display the image. A specific example is shown in Figure 6.

[0305] FIG. 6A illustrates a television device according to one embodiment of the present invention, which includes a housing 611, a support base 612, a display The television set includes a display unit 613, a speaker unit 614, a video input terminal 615, etc. Therefore, the light emitting device of the present invention can be applied to the display portion 613. Since the light emitting device of the present invention has a feature of being able to obtain high light emitting efficiency, This makes it possible to obtain a television set with reduced power consumption.

[0306] FIG. 6B shows a computer according to one embodiment of the present invention, which includes a main body 621, a housing 622, a display 623, a keyboard 624, an external connection port 625, a pointing device 626, etc. In this computer, the light emitting device of the present invention is applied to the display unit 623. The light emitting device of the present invention has a feature that high light emitting efficiency can be obtained. Therefore, a computer with reduced power consumption can be obtained by applying the light emitting device of the present invention. can be done.

[0307] FIG. 6C shows a mobile phone according to one embodiment of the present invention, which includes a main body 631, a housing 632, a display unit 6 33, audio input unit 634, audio output unit 635, operation keys 636, external connection port 637, In this mobile phone, the display unit 633 includes a light-emitting device according to the present invention. The light emitting device of the present invention has a feature that high light emitting efficiency can be obtained. Therefore, by applying the light emitting device of the present invention, a mobile phone with reduced power consumption can be manufactured. can be obtained.

[0308] FIG. 6D shows a camera according to one embodiment of the present invention, which includes a main body 641, a display unit 642, and a housing 64. 3, external connection port 644, remote control receiver 645, image receiver 646, battery 647, The camera includes a voice input unit 648, an operation key 649, an eyepiece unit 650, etc. The light emitting device of the present invention can be applied to the portion 642. Since the light emitting device of the present invention has the characteristic of being able to obtain high light efficiency, A camera with reduced power consumption can be obtained.

[0309] As described above, the light-emitting device according to one embodiment of the present invention has an extremely wide range of application. The light emitting device of the present invention can be applied to electronic devices in various fields. Thus, an electronic device with reduced power consumption can be obtained.

[0310] The light-emitting device according to one embodiment of the present invention can also be used as a lighting device. This is an example in which a light emitting device formed by applying the embodiment is used as an indoor lighting device 701. The light-emitting device shown in the above embodiment mode can be made large in area, and therefore can be used as a large-area lighting device. The light-emitting device described in the above embodiment can be used as a desk lamp 70. It is also possible to use it as 0. Note that the lighting fixtures include ceiling-mounted lighting fixtures and tabletop lighting fixtures. In addition to the fixtures, wall-mounted lighting fixtures, interior lighting, emergency exit lights, etc. are also included. The light emitting device formed by applying the above-mentioned embodiment has a long-life light emitting element, and therefore can provide long-life illumination. It is possible to use it as a device.

[0311] Note that this embodiment mode can be used in appropriate combination with the structures shown in other embodiment modes. It is decided that. EXAMPLES

[0312] In this example, the N,N'-bis(diphenyl ether) compound represented by the structural formula (G6-1) shown in the second embodiment is Benzofuran-4-yl)-N,N'-diphenyl-pyrene-1,6-diamine (abbreviation: An example of producing 1,6FrAPrn-II is shown below.

[0313] [ka]

[0314] [Step 1: N-(dibenzofuran-4-yl)-N-phenyl-amine (abbreviation: Fr Synthesis method of A-II)

[0315] 4-Iododibenzofuran 4.5g (15.4mmol), sodium tert-butoxide Add 4.5 g (4.6 mmol) of 1,000 g of dimethyl ether (DMSO) to a 300 mL three-neck flask and purify the flask with nitrogen. To this mixture, 98.0 mL of toluene and 2.8 mL of aniline (19.1 mmol) were added. ), and 0.3 mL of a 10% hexane solution of tri(tert-butyl)phosphine was added.

[0316] The mixture was heated to 60° C. and 54.1 ml of bis(dibenzylideneacetone)palladium(0) was added. g (0.1 mmol) was added, and the mixture was stirred at 80°C for 6.5 hours. After stirring, (Wako Pure Chemical Industries, Ltd., Catalog Number: 540-00135), Celite (Wako Pure Chemical Industries, Ltd. (Cat. No. 531-16855), suction filtered through alumina, and the filtrate obtained.

[0317] The filtrate was concentrated to obtain a solid. The solid was purified by silica gel column chromatography. The fraction was purified using a 5:1 hexane / toluene developing solvent. Concentration gave the desired white solid, 3.3 g, 84% yield. is shown below in (B1-1).

[0318] [ka]

[0319] Nuclear magnetic resonance (NMR) analysis confirmed that this compound was the target compound, N-(dibenzofuran-4 -yl)-N-phenyl-amine (abbreviation: FrA-II).

[0320] The obtained compound 1 The 1 H NMR data is shown below. 1 H NMR (CDCl3,300MHz): δ=6.20(s, 1H), 6.98-7 .03(m, 1H), 7.21-7.59(m, 10H), 7.95(d, J=7.8H z, 1H)

[0321] Also, 1 The H NMR charts are shown in Figures 8(A) and (B). This is a chart showing an expanded range of 6.00 ppm to 8.25 ppm in A).

[0322] [Step 2: N,N'-bis(dibenzofuran-4-yl)-N,N'-diphenyl- Synthesis method of pyrene-1,6-diamine (abbreviation: 1,6FrAPrn-II)

[0323] 1,6-Dibromopyrene 0.8g (2.1mmol), N-(dibenzofuran-4-yl) )-N-phenyl-amine 1.1g (4.2mmol), sodium tert-butoxide Put 0.6 g (6.2 mmol) of cid into a 50 mL three-neck flask and replace the atmosphere in the flask with nitrogen. To this mixture, 20.0 mL of toluene and 10 mL of tri(tert-butyl)phosphine were added. 0.3 mL of % hexane solution was added.

[0324] The mixture was heated to 60° C. and 46.7 ml of bis(dibenzylideneacetone)palladium(0) was added. g (0.1 mmol) was added, and the mixture was stirred at 80°C for 3.0 hours. After stirring, The mixture was filtered through celite and alumina under suction to obtain a filtrate.

[0325] The filtrate was concentrated to obtain a solid. The solid was purified by silica gel column chromatography. The fraction was purified using a hexane:toluene (7:3) developing solvent. The concentrated solid was recrystallized from chloroform and hexane to give the desired yellow solid. The solid was obtained in 0.7 g, 45% yield.

[0326] The resulting yellow solid (0.6 g) was purified by train sublimation. The purification conditions were: pressure 3.1 Pa, argon gas flow rate 4.0 mL / min, 3 The yellow solid was heated at 0.05° C. After purification by sublimation, 0.5 g of a yellow solid was obtained with a recovery rate of 83%. The synthetic scheme of the above step 2 is shown below (B1-2).

[0327] [ka]

[0328] The compounds synthesized in the above steps were analyzed by nuclear magnetic resonance (NMR) and MS spectroscopy. However, the target product, N,N'-bis(dibenzofuran-4-yl)-N,N'-diphenyl -pyrene-1,6-diamine (abbreviation: 1,6FrAPrn-II) .

[0329] The obtained compound 1 The 1 H NMR data is shown below. 1 H NMR (CDCl3,300MHz): δ=6.86(d, J=7.8Hz, 4H ), 6.93(t, J=7.2Hz, 2H), 7.11-7.22(m, 8H), 7.3 1-7.41(m, 6H), 7.70(d, J=6.8Hz, 2H), 7.88-7.9 7(m, 6H), 8.08(d, J=8.4Hz, 2H), 8.25(d, J=9.0H z, 2H)

[0330] Also, 1 The H NMR charts are shown in Figures 9(A) and (B). This is an expanded chart showing the range of 6.75 ppm to 8.50 ppm in A).

[0331] The compounds obtained were analyzed by electrospray ionization mass spectrometry. Measurement of ESI-MS spectra The results are shown below. MS (ESI-MS): m / z=717 (M+H) + ;C 52 H 32 N2O2(716. twenty five)

[0332] The absorption spectrum of 1,6FrAPrn-II in toluene solution is shown in Figure 10(A). The emission spectrum is shown in Fig. 10(B). The absorption spectrum is shown in FIG. 11(A) and the emission spectrum is shown in FIG. 11(B). The spectra were measured using an ultraviolet-visible spectrophotometer (V550, manufactured by JASCO Corporation). The optical spectrum was measured using a fluorometer (FS920, manufactured by Hamamatsu Photonics, Inc.). The solution was placed in a quartz cell, and the thin film was evaporated onto a quartz substrate to prepare a sample for measurement. The absorption spectra shown in Figs. 10(A) and 11(A) are reference spectra. The reference spectrum in FIG. 10(A) is the absorption spectrum of quartz. This is an absorption spectrum measured by putting only toluene in the cell. The reference spectrum is the absorption spectrum of a quartz substrate. In the figure, the horizontal axis represents the wavelength (nm) and the vertical axis represents the intensity (arbitrary units). Absorption was observed around 1 nm, and the maximum emission wavelength was 450 nm (excitation wavelength 370 nm). In the case of the thin film, absorption is observed around 430 nm, and the emission spectrum peaks at 46 1, 488 nm (excitation wavelength 428 nm).

[0333] These results indicate that the Stokes shift of 1,6FrAPrn-II in toluene solution is was confirmed to be as small as 29 nm.

[0334] In addition, the HOMO and LUMO levels of 1,6FrAPrn-II in a thin film state were measured. The HOMO level was measured by photoelectron spectroscopy in air (Riken Keiki Co., Ltd., AC-2). The ionization potential was calculated by converting the measured ionization potential to a negative value. The level values ​​are shown in the absorption spectrum of the thin film of 1,6FrAPrn-II in Fig. 11(B). Using the data, the absorption edge is calculated from the Tauc plot assuming a direct transition, and the absorption edge is The energy gap was obtained by adding the value of the HOMO level to the energy gap of the The HOMO level of 1,6FrAPrn-II is -5.57 eV, and the energy gap The peak energy was 2.72 eV and the LUMO level was −2.85 eV.

[0335] Next, the redox reaction characteristics were investigated by cyclic voltammetry (CV) measurements. The measurement was performed using an electrochemical analyzer (manufactured by BAS Co., Ltd., model number: ALS model 600). The measurement method is described in detail below.

[0336] (Calculation of potential energy relative to the vacuum level of the reference electrode) First, the reference electrode (Ag / Ag + Potential of the electrode relative to the vacuum level The energy (eV) was calculated. That is, Ag / Ag + The Fermi level of the electrode was calculated. The redox potential of ferrocene in methanol is +0.610 vs. the standard hydrogen electrode. It is known that [V vs. SHE] (Reference: Christian R .Goldsmith et al., J.Am.Chem.Soc., Vol.1 24, No.1, 83-96, 2002). On the other hand, when the reference electrode used in this example was used, The redox potential of ferrocene in methanol was calculated to be +0.11V[v s.Ag / Ag + Therefore, the potential energy of this reference electrode is It was confirmed that the potential was 0.50 eV lower than the standard hydrogen electrode.

[0337] Here, the potential energy of the standard hydrogen electrode from the vacuum level is -4.44 eV. It is known that (References: Toshihiro Ohnishi and Tamami Koyama, Polymer EL Materials (Kyoritsu Shuppan), From the above, the potential energy of the reference electrode relative to the vacuum level is The energy was calculated to be -4.44-0.50=-4.94[eV].

[0338] (CV measurement of the target object) The solution used in the CV measurement was dehydrated dimethylformamide (DMF) (Aldrich Co., Ltd.) as the solvent. A supporting electrolyte (Drich, 99.8%, Catalog No. 22705-6) was used. Tetra-n-butylammonium chlorate (n-Bu4NClO4) (Tokyo Chemical Industry Co., Ltd.) Catalog number: T0836) was dissolved to a concentration of 100 mmol / L, and then the measurement was performed. The target substance was dissolved to a concentration of 2 mmol / L. The electrode was a platinum electrode (PTE platinum electrode, manufactured by BAS Co., Ltd.), and the auxiliary electrode was a platinum electrode. The electrode (Pt counter electrode (5 cm) for VC-3, manufactured by BAS Co., Ltd.) was placed at the reference electrode. The electrode is Ag / Ag + Electrode (RE7 non-aqueous solvent reference electrode, manufactured by BAS Co., Ltd.) The measurements were carried out at room temperature (20 to 25°C). The scan speed was standardized to 0.1 V / sec.

[0339] Using this solution, CV measurement of the target substance was performed. The potential of the working electrode relative to the reference electrode was set to -0 After scanning from .10V to 1.50V, it scanned from 1.50V to -0.10V. After 100 cycles of scanning, a clear peak indicating oxidation was observed. The peak shape hardly changed even after 1,6FrAPrn- II exhibits good properties in terms of repeated oxidation-reduction between the oxidized and neutral states. was confirmed.

[0340] In this CV measurement, the oxidation peak potential (from neutral to oxidation) E pa is 0.58 V. The reduction peak potential (between the oxidation side and neutral side) E pc was 0.46V. Therefore, the half-wave potential (E pa and E pc The intermediate potential, (E pa +E pc ) / 2[V]) This means that 1,6FrAPrn-II has a voltage of 0.52[V v s.Ag / Ag + ] is oxidized by the electrical energy of As shown above, the potential energy of the reference electrode relative to the vacuum level is -4.94[ eV], so the HOMO level of 1,6FrAPrn-II is -4.94-0.52 =-5.46[eV].

[0341] Thermogravimetry-differential thermal analysis (TG-DTA) of the obtained 1,6FrAPrn-II mogravimetry-Differential Thermal Analyses The measurements were carried out using a high vacuum differential thermobalance (Bruker AXS Co., Ltd.). The temperature was increased at normal pressure, at a rate of 10°C / min, and nitrogen gas was used. When measurements were taken under the conditions below (flow rate 200 mL / min), the relationship between weight and temperature (thermogravimetric measurement) ) the 5% weight loss temperature was 420°C, indicating good heat resistance. EXAMPLES

[0342] In this example, N,N'-bis(dibenzothiophene-4) represented by structural formula (G6-2) was -yl)-N,N'-diphenyl-pyrene-1,6-diamine (abbreviation: 1,6ThAPr An example of producing n-II) is shown below.

[0343] [ka]

[0344] [Step 1: N-(dibenzothiophen-4-yl)-N-phenyl-amine (abbreviation: Synthesis method of ThA-II]

[0345] 4-Iododibenzothiophene 4.7g (15.3mmol), sodium tert- Put 4.5g (4.6mmol) of butoxide into a 300mL three-neck flask and The mixture was purged with nitrogen. 98.0 mL of toluene and 2.7 mL (18.3 mm ol), and 0.3 mL of a 10% hexane solution of tri(tert-butyl)phosphine was added. .

[0346] The mixture was heated to 60°C and 69.8 ml of bis(dibenzylideneacetone)palladium(0) was added. g (0.1 mmol) was added, and the mixture was stirred at 80°C for 14 hours. After stirring, The mixture was filtered through celite and alumina with suction to obtain a filtrate.

[0347] The filtrate was concentrated to obtain a solid. The solid was purified by silica gel column chromatography. The fraction was purified using a 4:1 hexane / toluene developing solvent. The product was concentrated to give 3.9 g of the target product in a yield of 90%. The synthesis scheme for step 1 above is shown below. Shown in (B2-1).

[0348] [ka]

[0349] Nuclear magnetic resonance (NMR) analysis confirmed that the compound synthesized in the above step was N-(dibenzo-p-(1,2-diphenyl-2,4-diphenyl- ... It was confirmed that the compound was thiophene-4-yl-N-phenyl-amine (abbreviation: ThA-II). I acknowledged.

[0350] The obtained compound 1 The 1 H NMR data is shown below. 1 H NMR (CDCl3,300MHz): δ=5.66(s, 1H), 6.95-7 .00(m, 1H), 7.07-7.10(m, 2H), 7.27-7.50(m, 6H ), 7.83-7.89(m, 2H), 8.13-8.19(m, 1H)

[0351] Also, 1 The H NMR charts are shown in Figures 12(A) and (B). This is a chart showing an expanded range of 5.50 ppm to 8.25 ppm in 12(A). be.

[0352] [Step 2: N,N'-bis(dibenzothiophen-4-yl)-N,N'-diphenyl Synthesis method of ruthenium-pyrene-1,6-diamine (abbreviation: 1,6ThAPrn-II)

[0353] 1,6-Dibromopyrene 0.7g (2.0mmol), N-(dibenzothiophene-4- 1.1g (4.0mmol) of N-phenyl-amine, sodium tert-butyl Put 0.6 g (6.0 mmol) of thionate into a 300 mL three-neck flask and fill the flask with nitrogen. To this mixture was added 20.0 mL of toluene and tri(tert-butyl)phosphine. 0.3 mL of a 10% hexane solution was added.

[0354] The mixture was heated to 60° C. and 40.3 ml of bis(dibenzylideneacetone)palladium(0) was added. g (0.1 mmol) was added, and the mixture was stirred at 80°C for 3.5 hours. After stirring, chloroform was added. Add 400 mL, filter through Florisil, Celite, and alumina with suction to obtain the filtrate. .

[0355] The filtrate was concentrated to obtain a solid. The solid was purified by silica gel column chromatography. The fraction was purified using a hexane:toluene (7:3) developing solvent. Concentrated.

[0356] The solid obtained by concentration was recrystallized with chloroform and hexane to obtain the desired yellow solid in 0. 6g was obtained in a yield of 39%. The resulting yellow solid (0.6g) was subjected to train sublimation. The sublimation purification was carried out under the following conditions: pressure 2.5 Pa, argon gas flow rate 5.0 mL The yellow solid was heated at 313°C while flowing at 0. 5g was obtained with a recovery rate of 82%. The synthesis scheme of step 2 above is shown below (B2-2). .

[0357] [ka]

[0358] The compounds synthesized in the above steps were analyzed by nuclear magnetic resonance (NMR) and MS spectroscopy. The target product is N,N'-bis(dibenzothiophen-4-yl)-N,N'-diphenyl It was confirmed that the compound was 1,6-thylene-1,6-diamine (abbreviation: 1,6ThAPrn-II). Ta.

[0359] The obtained compound 1 The 1 H NMR data is shown below. 1 H NMR (CDCl3,300MHz): δ=6.92-7.02(m, 6H), 7 .20-7.27(m, 6H), 7.35-7.46(m, 6H), 7.66-7.69 (m, 2H), 7.81(d, J=8.4Hz, 2H), 7.87(d, J=9.0Hz , 2H), 7.96(d, J=7.8Hz, 2H), 8.03(d, J=8.4Hz, 2 H), 8.15-8.18(m, 4H)

[0360] Also, 1The H NMR charts are shown in Figures 13(A) and (B). This is a chart showing an expanded range of 6.75 ppm to 8.25 ppm in 13(A). be.

[0361] The results of measuring the MS spectrum of the obtained compound are shown below. MS (ESI-MS): m / z=748 (M+H) + ;C 52 H 32 N2S2(748. 2)

[0362] The absorption spectrum of 1,6ThAPrn-II in a toluene solution is shown in FIG. The emission spectrum is shown in FIG. 14(B). The absorption spectrum is shown in FIG. 15(A) and the emission spectrum is shown in FIG. 15(B). The spectra and emission spectra were measured using the same apparatus and method as in Example 1. The absorption spectra in FIG. 14(A) and FIG. 15(A) are the same as those in Example 1. The absorption spectrum is the same as that of the reference spectrum. In the figure, the horizontal axis represents the wavelength (nm) and the vertical axis represents the intensity (arbitrary units). Absorption was observed around 4 nm, and the maximum emission wavelength was 455 nm (excitation wavelength 370 nm). In the case of the thin film, absorption is observed around 432 nm, and the emission spectrum peaks at 48 3, 501 nm (excitation wavelength 438 nm).

[0363] These results indicate that the Stokes shift of 1,6ThAPrn-II in toluene solution is It was confirmed that the size was as small as 31 nm.

[0364] In addition, we measured the HOMO and LUMO levels of 1,6ThAPrn-II in a thin film state. The measurement was carried out using the same apparatus and method as in Example 1. As a result, 1,6ThAPr The HOMO level of n-II is -5.49 eV and the energy gap is 2.69 e V and the LUMO level was −2.80 eV.

[0365] The redox reaction characteristics were examined by CV measurement in the same manner as in Example 1.

[0366] In the CV measurement of this example, the potential of the working electrode relative to the reference electrode was changed from -0.10 V to 0. After scanning to 6V, the voltage was scanned from 0.6V to -0.10V, indicating oxidation. A clear peak was observed. Moreover, the peak remained even after 100 cycles of scanning. The shape of 1,6ThAPrn-II hardly changed. It was confirmed that the material exhibits good characteristics with respect to repeated oxidation and reduction between the neutral state and the positive electrode.

[0367] In this CV measurement, the oxidation peak potential (from neutral to oxidation) E pa is 0.59 V. The reduction peak potential (between the oxidation side and neutral side) E pc was 0.48V. Therefore, the half-wave potential (E pa and E pc The intermediate potential, (E pa +E pc ) / 2[V]) This means that 1,6ThAPrn-II has a voltage of 0.54[V v s.Ag / Ag + ] is oxidized by the electrical energy of As shown above, the potential energy of the reference electrode relative to the vacuum level is -4.94[ eV], so the HOMO level of 1,6ThAPrn-II is -4.94-0.54 =-5.48[eV].

[0368] For 1,6ThAPrn-II, the thermal weight was measured using the same apparatus and measurement method as in Example 1. The weight and temperature relationship (thermogravimetry) was used to determine the mass of 1,6ThAPr The 5% weight loss temperature of n-II was 458°C, indicating good heat resistance. EXAMPLES

[0369] In this example, N,N'-bis(dibenzofuran-2) represented by the structural formula (G10-1) is -yl)-N,N'-diphenyl-pyrene-1,6-diamine (abbreviation: 1,6FrAPr An example of manufacturing n) is shown below.

[0370] [ka]

[0371] 1,6-Dibromopyrene 0.9g (2.5mmol), N-(dibenzofuran-2-yl )-N-phenyl-amine 1.3g (5.0mmol), sodium tert-butoxide Put 0.7 g (7.4 mmol) of cid into a 100 mL three-neck flask and place the flask under nitrogen. Exchanged.

[0372] To this mixture was added 25.0 mL of toluene and 10 mL of tri(tert-butyl)phosphine. 0.3 mL of 100% hexane solution was added. The mixture was heated to 80° C. and bis(dibenzylidene azathioprine) was added. 34.9 mg (0.06 mmol) of palladium(0) was added and the mixture was stirred for 7 hours. After stirring, the mixture was suction filtered through Florisil, Celite, and alumina to obtain a filtrate.

[0373] The filtrate was concentrated and the resulting solid was separated by silica gel column chromatography (eluent: hexane). The mixture was purified using a solvent mixture of hexane:toluene (7:3) and the obtained fraction was concentrated. The solid was recrystallized from toluene and hexane to obtain 1.3 g of the desired yellow solid in a yield of 71%. Obtained in %.

[0374] The resulting yellow solid (1.2 g) was purified by train sublimation. The preparation conditions were a pressure of 2.4 Pa, argon gas at a flow rate of 5.0 mL / min, and 3 The yellow solid was heated at 0.2°C. After purification by sublimation, 1.1g of yellow prism crystals were obtained, with a recovery rate of 90%. The synthesis scheme of the above synthesis example is shown below in (C1-1).

[0375] [ka]

[0376] The compounds synthesized in the above steps were analyzed by nuclear magnetic resonance (NMR) and MS spectroscopy. The target compound is N,N'-bis(dibenzofuran-2-yl)-N,N'-diphenyl- It was confirmed to be pyrene-1,6-diamine (abbreviation: 1,6FrAPrn).

[0377] The obtained compound 1 The 1 H NMR data is shown below. 1 H NMR (CDCl3,300MHz): δ=6.94(t, J=6.9Hz, 2H ), 7.02(d, J=7.8Hz, 4H), 7.15-7.46(m, 12H), 7. 53(d, J=8.4Hz, 2H), 7.72-7.75(m, 4H), 7.82-7. 86(m, 2H), 7.90-7.93(m, 2H), 8.09-8.14(m, 2H) , 8.17-8.23(m, 2H)

[0378] Also,1 The H NMR charts are shown in Figures 16(A) and (B). This is a chart showing an expanded range of 6.75 ppm to 8.00 ppm in 16(A). be.

[0379] The results of measuring the MS spectrum of the obtained compound are shown below. MS (ESI-MS): m / z=717 (M+H) + ;C 52 H 32 N2O2(716. twenty five)

[0380] The absorption spectrum of 1,6FrAPrn in toluene solution is shown in Figure 17(A). The optical spectrum is shown in Figure 17(B). The absorption spectrum and the emission spectrum are shown in Fig. 18(A) and Fig. 18(B). The emission spectrum was measured using the same device and method as in Example 1. The absorption spectra of FIG. 18(A) and FIG. 18(A) are the same as those of the reference samples in Example 1. The absorption spectrum is the spectrum obtained by subtracting the horizontal spectrum. The axis represents wavelength (nm) and the vertical axis represents intensity (arbitrary units). In the case of a toluene solution, 434 nm Absorption was observed around the wavelength of 465 nm (excitation wavelength 370 nm). In the case of the thin film, absorption is observed around 441 nm, and the emission spectrum peaks at 480 and 5 08 nm (excitation wavelength 441 nm).

[0381] From these results, the Stokes shift of 1,6FrAPrn in toluene solution is 31 It was confirmed that the particle size was as small as nm.

[0382] We also carried out measurements of the HOMO and LUMO levels of 1,6FrAPrn in a thin film state. The same apparatus and method were used as in Example 1. As a result, H of 1,6FrAPrn The OMO level is -5.48 eV, the energy gap is 2.64 eV, and the L The UMO level was -2.84 eV.

[0383] The redox reaction characteristics were examined by CV measurement in the same manner as in Example 1.

[0384] In the CV measurement of this example, the potential of the working electrode relative to the reference electrode was changed from -0.10 V to 0 After scanning to 0.6V, the voltage was scanned from 0.6V to -0.10V, showing no oxidation. A clear peak was observed. Even after 100 cycles of scanning, the peak This indicates that 1,6FrAPrn is in the oxidized state and in the intermediate state. It was confirmed that the material exhibits good characteristics with respect to repeated oxidation-reduction between the active and passive states.

[0385] In this CV measurement, the oxidation peak potential (from neutral to oxidation) E pa is 0.48 V. The reduction peak potential (between the oxidation side and neutral side) E pc was 0.40V. Therefore, the half-wave potential (E pa and E pc The intermediate potential, (E pa +E pc ) / 2[V]) This means that 1,6FrAPrn is 0.44 [V vs.A g / Ag + [The electric energy of the above-mentioned The potential energy of the reference electrode relative to the vacuum level is -4.94 eV. Therefore, the HOMO level of 1,6FrAPrn is -4.94-0.44=-5.38 It was confirmed that the value was [eV].

[0386] Thermogravimetry was performed on 1,6FrAPrn using the same apparatus and method as in Example 1. -Differential thermal analysis was performed. From the relationship between weight and temperature (thermogravimetry), the obtained 1,6FrAP The 5% weight loss temperature of rn was 448°C, indicating good heat resistance. EXAMPLES

[0387] In this example, N,N'-bis(dibenzothiophene) represented by the structural formula (G10-2) -2-yl)-N,N'-diphenyl-pyrene-1,6-diamine (abbreviation: 1,6ThA An example of manufacturing Prn is shown below.

[0388] [ka]

[0389] 1,6-Dibromopyrene 0.9g (2.4mmol), N-(dibenzothiophene-2- 1.3 g (4.8 mmol) of N-phenyl-amine, sodium tert-butyl Put 0.7 g (7.0 mmol) of toxoside into a 50 mL three-neck flask and fill the flask with nitrogen. Replaced.

[0390] Add 25.0 mL of toluene and 10% hexanediaminetetraacetate to the mixture. 0.2 mL of the dimethylformamide solution was added. The mixture was heated to 80° C. and bis(dibenzylideneacetone) ) Palladium(0) (25.7 mg, 0.04 mmol) was added and the mixture was stirred for 2.0 hours.

[0391] After stirring, the mixture was brought to 90°C and bis(dibenzylideneacetone)palladium(0)26 was added. After stirring, the mixture was heated to 80° C. Add 0.2 mL of a 10% hexane solution of tri(tert-butyl)phosphine and stir for 1.0 h. After stirring, the mixture was heated to 85° C. and stirred for 3.5 hours. The mixture was filtered through suction through celite, then through alumina to obtain a filtrate.

[0392] The filtrate was concentrated and the resulting solid was separated by silica gel column chromatography (eluent: hexane). The resulting fraction was concentrated to give a yellow solid. The obtained solid was recrystallized from toluene and hexane to give 0.6 g of a yellow solid. The yield was 34%.

[0393] The resulting yellow solid (0.6 g) was purified by train sublimation. The preparation conditions were a pressure of 2.5 Pa, argon gas at a flow rate of 5.0 mL / min, and 3 The yellow solid was heated at 00°C. After purification by sublimation, 0.4 g of the desired yellow prism crystal was recovered. The synthesis scheme of the above synthesis example is shown below (C2-1).

[0394] [ka]

[0395] The compounds synthesized in the above steps were analyzed by nuclear magnetic resonance (NMR) and MS spectroscopy. However, the target product, N,N'-bis(dibenzothiophene-2-yl)-N,N'-diphenyl It was confirmed that the compound was 1,6-thyl-pyrene-1,6-diamine (abbreviation: 1,6ThAPrn).

[0396] The obtained compound 1 The 1 H NMR data is shown below. 1 H NMR (CDCl3,300MHz): δ=6.95-7.00(m, 2H), 7 .08-7.11(m, 4H), 7.02-7.42(m, 10H), 7.68(d, J =8.1Hz, 2H), 7.80-7.94(m, 10H), 8.11(d, J=8.4 Hz, 2H), 8.21(d, J=9.3Hz, 2H)

[0397] Also, 1 The H NMR charts are shown in Figures 19(A) and (B). This is a chart showing an expanded range of 6.75 ppm to 8.50 ppm in 19(A). be.

[0398] The results of measuring the MS spectrum of the obtained compound are shown below. MS (ESI-MS): m / z=749 (M+H) + ;C 52 H 32 N2S2(748. 2)

[0399] The absorption spectrum of 1,6ThAPrn in toluene solution is shown in Figure 20(A). The optical spectrum is shown in Figure 20(B). The absorption spectrum and the emission spectrum are shown in FIG. The emission spectrum was measured using the same device and method as in Example 1. The absorption spectra of FIG. 21(A) and FIG. 21(A) are the same as those of the reference sample in Example 1. The absorption spectrum is the one obtained by subtracting the absorption spectrum from the horizontal spectrum in Figs. The axis represents wavelength (nm) and the vertical axis represents intensity (arbitrary units). In the case of a toluene solution, 436 nm Absorption was observed around the wavelength of 467 nm (excitation wavelength 370 nm). In the case of a thin film, absorption is observed around 445 nm, and the maximum emission wavelength is 563 nm (excitation wavelength 445 nm).

[0400] From these results, the Stokes shift of 1,6ThAPrn in toluene solution is 31n It was confirmed that the mass ratio was small, only about m.

[0401] We also carried out measurements of the HOMO and LUMO levels of 1,6ThAPrn in a thin film state. The same apparatus and measurement method as in Example 1 were used. As a result, H of 1,6ThAPrn The OMO level is -5.48 eV, the energy gap is 2.61 eV, and the L The UMO level was -2.87 eV.

[0402] The redox reaction characteristics were examined by CV measurement in the same manner as in Example 1.

[0403] In the CV measurement of this example, the potential of the working electrode relative to the reference electrode was changed from -0.10 V to 0 After scanning to 0.6V, the voltage was scanned from 0.6V to -0.10V, showing no oxidation. A clear peak was observed. Even after 100 cycles of scanning, the peak This indicates that 1,6ThAPrn is in the oxidized state and in the intermediate state. It was confirmed that the material exhibits good characteristics with respect to repeated oxidation-reduction between the active and passive states.

[0404] In this CV measurement, the oxidation peak potential (from neutral to oxidation) E pa is 0.49 V. The reduction peak potential (between the oxidation side and neutral side) E pc was 0.40V. Therefore, the half-wave potential (E pa and E pc The intermediate potential, (E pa +E pc ) / 2[V]) This means that 1,6ThAPrn has a voltage of 0.45 [V vs.A g / Ag + [The electric energy of the above-mentioned The potential energy of the reference electrode relative to the vacuum level is -4.94 eV. Therefore, the HOMO level of 1,6ThAPrn is -4.94-0.45=-5.39 It was confirmed that the value was [eV].

[0405] Thermogravimetry was performed on 1,6ThAPrn using the same apparatus and method as in Example 1. -Differential thermal analysis was performed. From the relationship between weight and temperature (thermogravimetry), 5 The % weight loss temperature was 468°C, indicating good heat resistance. EXAMPLES

[0406] In this example, N,N'-bis[3-(dibenzofuran)] represented by structural formula (G7-1) is -4-yl)phenyl]-N,N'-diphenyl-pyrene-1,6-diamine (abbreviation: 1 An example of the production of 6mFrBAPrn-II is shown below.

[0407] [ka]

[0408] [Step 1: Synthesis of 3-(dibenzofuran-4-yl)-diphenylamine]

[0409] 2.5 g (7.7 mmol) of 4-(3-bromophenyl)dibenzofuran and sodium Put 2.1 g (21.6 mmol) of tert-butoxide into a 200 mL three-neck flask. The atmosphere in the flask was replaced with nitrogen.

[0410] This mixture was diluted with 50.0 mL of toluene, 0.7 mL (7.6 mmol) of aniline and tri(t 0.2 mL of a 10% hexane solution of (ert-butyl)phosphine was added. The temperature was adjusted to 5°C, and 42.5 mg (0.1 mm ol) was added, the temperature was raised to 80° C., and the mixture was stirred for 2.0 hours.

[0411] After stirring, the mixture was filtered through Florisil, Celite, and alumina under suction to obtain a filtrate. The filtrate was concentrated to give an oily substance, which was then purified by silica gel column chromatography (eluent: hexane). The mixture was purified using a solvent mixture of toluene (3:2) to give 2.4 g of an oily product in a yield of 91%. The synthesis scheme of Group 1 is shown below (D1-1).

[0412] [ka]

[0413] [Step 2: N,N'-bis[3-(dibenzofuran-4-yl)phenyl]-N,N '-Diphenyl-pyrene-1,6-diamine (abbreviation: 1,6mFrBAPrn-II) Synthesis method]

[0414] 0.6 g (1.5 mmol) of 1,6-dibromopyrene and sodium tert-butoxy 0.5 g (4.7 mmol) of dimethylformamide was placed in a 50 mL three-neck flask, and the atmosphere in the flask was replaced with nitrogen. To this mixture, 2.2 mL of toluene and 15.0 mL of 3-(dibenzo-p-toluidine) 1.0 g (3.1 mmol) of tri(tert-furan-4-yl)-diphenylamine 0.2 mL of a 10% hexane solution of (butyl)phosphine was added.

[0415] The mixture was heated to 60° C. and 41.2 ml of bis(dibenzylideneacetone)palladium(0) was added. g (0.1 mmol) was added, and the mixture was stirred at 80°C for 2 hours. After stirring, the mixture was filtered by suction to obtain a solid. Got a body.

[0416] 500 mL of toluene was added to the obtained solid, heated to 110°C, and then separated into Florisil and Celite. The mixture was filtered through alumina under suction to obtain a filtrate. The filtrate was concentrated to obtain a solid. To the solid was added 45 mL of toluene and heated.

[0417] The mixture was filtered under suction to obtain 0.8 g of a yellow solid in a yield of 65%. The yellow solid was purified by train sublimation. The conditions for purification were pressure 2 A yellow solid was precipitated at 305°C under argon gas at a flow rate of 4.0 mL / min and a pressure of 0.4 Pa. After purification by sublimation, 0.6 g of a yellow solid was obtained with a recovery rate of 73%. The synthesis scheme is shown below (D1-2).

[0418] [ka]

[0419] The compounds synthesized in the above steps were analyzed by nuclear magnetic resonance (NMR) and MS spectroscopy. The product is the target product, N,N'-bis[3-(dibenzofuran-4-yl)phenyl]-N, N'-Diphenyl-pyrene-1,6-diamine (abbreviation: 1,6mFrBAPrn-II) It was confirmed that.

[0420] The obtained compound 1 The 1 H NMR data is shown below. 1 H NMR (CDCl3,300MHz): δ=6.98-7.03(m, 2H), 7 .09-7.14(m, 4H), 7.19-7.39(m, 16H), 7.48-7.5 1(m, 4H), 7.70(t, J=1.8Hz, 2H), 7.82-7.87(m, 4 H), 7.92(d, J=8.1Hz, 2H), 7.98(d, J=9.3Hz, 2H) , 8.15(d, J=8.4Hz, 2H), 8.27(d, J=9.0Hz, 2H)

[0421] Also, 1 The H NMR charts are shown in Figures 22(A) and (B). This is a chart showing an expanded range of 6.75 ppm to 8.50 ppm in 22(A). be.

[0422] The results of measuring the MS spectrum of the obtained compound are shown below. MS (ESI-MS): m / z=869 (M+H) + ;C 64 H 40 N2O2(868. 31)

[0423] The absorption spectrum of 1,6mFrBAPrn-II in toluene solution is shown in Figure 23 ( The emission spectrum is shown in Figure 23(B). The absorption spectrum of the thin film is shown in FIG. 24(A), and the emission spectrum is shown in FIG. 24(B). The absorption spectrum and emission spectrum were measured using the same apparatus and method as in Example 1. The absorption spectra of FIG. 23(A) and FIG. 24(A) were obtained by As in Example 1, the reference spectrum was subtracted from the absorption spectrum. In FIG. 24, the horizontal axis represents wavelength (nm) and the vertical axis represents intensity (arbitrary unit). Toluene solution In the case of In the case of the thin film, absorption was observed around 437 nm, and the emission wavelength was 48 4, 501 nm (excitation wavelength 434 nm).

[0424] These results suggest that the Stokes-Schiff effect of 1,6mFrBAPrn-II in toluene solution It was confirmed that the size of the defect was as small as 30 nm.

[0425] In addition, the HOMO and LUMO levels of 1,6mFrBAPrn-II in the thin film state The measurement was performed using the same device and method as in Example 1. The result was 1.6 mFr The HOMO level of BAPrn-II is -5.51 eV, and the energy gap is 2 The optical density was 0.67 eV and the LUMO level was -2.84 eV.

[0426] The redox reaction characteristics were examined by CV measurement in the same manner as in Example 1.

[0427] In the CV measurement of this example, the potential of the working electrode relative to the reference electrode was changed from -0.10 V to 0 After scanning to 0.6V, the voltage was scanned from 0.6V to -0.10V, showing no oxidation. A clear peak was observed. Even after 100 cycles of scanning, the peak The shape of the 1,6mFrBAPrn-II was almost unchanged. It was confirmed that the compound exhibits good properties in the repeated oxidation-reduction between the oxidized and neutral states. came.

[0428] In this CV measurement, the oxidation peak potential (from neutral to oxidation) E pa is 0.52 V. The reduction peak potential (between the oxidation side and neutral side) E pc was 0.45V. Therefore, the half-wave potential (E pa and E pcThe intermediate potential, (E pa +E pc ) / 2[V]) This means that the 1,6mFrBAPrn-II is 0.49[V vs. Ag / Ag + ] is oxidized by electrical energy of As mentioned above, the potential energy of the reference electrode relative to the vacuum level is -4.9 4[eV], the HOMO level of 1,6mFrBAPrn-II is -4.94- It was confirmed that 0.49=-5.43[eV].

[0429] For 1,6mFrBAPrn-II, the same apparatus and measurement method as in Example 1 were used. Thermogravimetry - Differential thermal analysis was performed. The relationship between weight and temperature (thermogravimetry) was 1.6 mFr The 5% weight loss temperature of BAPrn-II was above 500°C, indicating good heat resistance. EXAMPLES

[0430] In this example, N,N'-bis[3-(dibenzothiophene)-2-(phenylalanine)-1,3-dimethylphenylsilyl] ... (phenyl-4-yl)phenyl)-N,N'-diphenyl-pyrene-1,6-diamine (abbreviation An example of the production of 1,6mThBAPrn-II is shown below.

[0431] [ka]

[0432] [Step 1: Synthesis of 3-(dibenzothiophen-4-yl)-diphenylamine]

[0433] 2.4 g (7.1 mmol) of 4-(3-bromophenyl)dibenzothiophene and sodium Add 2.0 g (20.9 mmol) of t-butoxide to a 200 mL three-neck flask. The atmosphere in the flask was replaced with nitrogen.

[0434] This mixture was diluted with 50.0 mL of toluene, 0.7 mL (7.6 mmol) of aniline and tri(t 0.2 mL of a 10% hexane solution of (ert-butyl)phosphine was added. The temperature was lowered to 0°C, and 42.7 mg (0.1 mm ol) was added, and the temperature was raised to 80° C. and the mixture was stirred for 5.0 hours.

[0435] After stirring, the mixture was filtered through Florisil, Celite, and alumina under suction to obtain a filtrate. The filtrate was concentrated to give an oily substance, which was then purified by silica gel column chromatography (eluent: hexane). The product was purified using an aqueous hexane / toluene ratio of 2:1 to obtain 2.4 g of the desired product in a yield of 95%. The synthesis scheme of compound 1 is shown below (D2-1).

[0436] [ka]

[0437] [Step 2: N,N'-bis[3-(dibenzothiophen-4-yl)phenyl]-N ,N'-Diphenyl-pyrene-1,6-diamine (abbreviation: 1,6mThBAPrn-II ) Synthesis method

[0438] 0.6 g (1.7 mmol) of 1,6-dibromopyrene and sodium tert-butoxy Put 0.5 g (5.2 mmol) of ethyl alcohol into a 50 mL three-neck flask and replace the atmosphere in the flask with nitrogen. To this mixture, 2.0 mL of toluene and 15.0 mL of 3-(dibenzo-p-toluidine) Thiophen-4-yl)-diphenylamine 1.2 g (3.3 mmol), tri(tert-butyl) 0.2 mL of a 10% hexane solution of t-butylphosphine was added.

[0439] The mixture was heated to 80° C. and 17.2 ml of bis(dibenzylideneacetone)palladium(0) was added. g (0.03 mmol) was added and stirred for 1.0 hour. After stirring, bis(dibenzylidene a Add 18.5 mg (0.03 mmol) of palladium(0) to the mixture and stir for 1.0 hour. Ta.

[0440] After stirring, 600 mL of toluene was added, and the mixture was filtered by suction through Florisil, Celite, and alumina. The filtrate was concentrated to give a solid.

[0441] To the obtained solid, 75 mL of toluene was added and heated. The mixture was suction filtered to give a yellow solid The yellow solid (0.6 g) was purified by train sublimation. The sublimation purification conditions were a pressure of 2.3 Pa and an argon gas flow rate of 6.0 mL / min. The yellow solid was heated at 308°C. After purification by sublimation, 0.5g of yellow solid was obtained, with a recovery rate of 77%. The synthesis scheme of step 2 above is shown below (D2-2).

[0442] [ka]

[0443] The compounds synthesized in the above steps were analyzed by nuclear magnetic resonance (NMR) and MS spectroscopy. N,N'-bis[3-(dibenzothiophen-4-yl)phenyl]-N,N'-di Phenyl-pyrene-1,6-diamine (abbreviation: 1,6mThBAPrn-II) It was confirmed that.

[0444] The obtained compound 1 The 1 H NMR data is shown below. 1H NMR (CDCl3,300MHz): δ=7.00-7.44(m, 28H), 7.90-7.97(m, 6H), 8.00(d, J=9.3Hz, 2H), 8.17( d, J=8.4Hz, 2H), 8.27(d, J=9.3Hz, 2H)

[0445] Also, 1 The H NMR charts are shown in Figures 25(A) and (B). This is a chart showing an expanded range of 6.75ppm to 8.50ppm in 25(A). be.

[0446] The results of measuring the MS spectrum of the obtained compound are shown below. MS (ESI-MS): m / z=901 (M+H) + ;C 64 H 40 N2S2(900. 26)

[0447] The absorption spectrum of 1,6mThBAPrn-II in a toluene solution is shown in Figure 26 ( The emission spectrum is shown in Figure 26(B). The absorption spectrum of the thin film is shown in FIG. 27(A), and the emission spectrum is shown in FIG. 27(B). The absorption spectrum and emission spectrum were measured using the same apparatus and method as in Example 1. The absorption spectra of FIG. 26(A) and FIG. 27(A) were obtained by As in Example 1, the reference spectrum is subtracted from the absorption spectrum. In 27, the horizontal axis represents wavelength (nm) and the vertical axis represents intensity (arbitrary units). In the case of a toluene solution Absorption is observed around 429 nm, and the maximum emission wavelength is 457 nm (excitation wavelength 370 nm). In the case of the thin film, absorption was observed around 438 nm, and the emission spectrum peak The emission wavelengths were 475 and 504 nm (excitation wavelength 432 nm).

[0448] These results suggest that the Stokes-Schiff effect of 1,6mThBAPrn-II in toluene solution The size was confirmed to be as small as 28 nm.

[0449] In addition, the HOMO and LUMO levels of 1,6mThBAPrn-II in the thin film state The measurement was carried out using the same equipment and method as in Example 1. The HOMO level of BAPrn-II is -5.51 eV, and the energy gap is 2 The optical density was 0.66 eV and the LUMO level was -2.85 eV.

[0450] The redox reaction characteristics were examined by CV measurement in the same manner as in Example 1.

[0451] In the CV measurement of this example, the potential of the working electrode relative to the reference electrode was changed from -0.10 V to 0 After scanning to 0.6V, the voltage was scanned from 0.6V to -0.10V, showing no oxidation. A clear peak was observed. Even after 100 cycles of scanning, the peak The shape of the crystal did not change much. This indicates that 1,6mThBAPrn-II is an acid. It was confirmed that the compound exhibits good properties in the repeated oxidation-reduction between the oxidized and neutral states. came.

[0452] In this CV measurement, the oxidation peak potential (from neutral to oxidation) E pa is 0.53 V. The reduction peak potential (between the oxidation side and neutral side) E pc was 0.45V. Therefore, the half-wave potential (E pa and E pc The intermediate potential, (E pa +E pc ) / 2[V]) This means that 1,6mThBAPrn-II has a voltage of 0.49[V vs. Ag / Ag + ] is oxidized by electrical energy of As mentioned above, the potential energy of the reference electrode relative to the vacuum level is -4.9 4[eV], the HOMO level of 1,6mThBAPrn-II is -4.94- It was confirmed that 0.49=-5.43[eV].

[0453] For 1,6mThBAPrn-II, the same apparatus and measurement method as in Example 1 were used. Thermogravimetry - Differential thermal analysis was carried out. From the relationship between weight and temperature (thermogravimetry), 1.6mTh The 5% weight loss temperature of BAPrn-II was above 500°C, indicating good heat resistance. EXAMPLES

[0454] In this example, N,N'-bis[4-(dibenzofuran)] represented by structural formula (G8-1) is -4-yl)phenyl]-N,N'-diphenyl-pyrene-1,6-diamine (abbreviation: 1 An example of the production of 6FrBAPrn-II is shown below.

[0455] [ka]

[0456] [Step 1: Synthesis of 4-(dibenzofuran-4-yl)diphenylamine]

[0457] 4-Bromodiphenylamine 1.8g (7.5mmol), (dibenzofuran-4-yl ) boronic acid 1.6g (7.5mmol), tris(2-methylphenyl)phosphine 0. 1 g (0.4 mmol) was placed in a 100 mL three-neck flask, and the atmosphere in the flask was replaced with nitrogen.

[0458] This mixture was diluted with 30.0 mL of toluene, 9.3 mL of ethanol, and an aqueous solution of potassium carbonate (2 mL Add 7.5 mL of 1000 mL of ethanol (7.5 mol / L) and degas the mixture by stirring while reducing the pressure inside the flask. Ta.

[0459] After degassing, the mixture was heated to 60°C, and then 41.2 mg (0.2 mmol) of palladium (II) acetate was added. The mixture was heated to 80° C. and refluxed at 80° C. for 3.0 hours. After refluxing, the mixture Toluene and water were added, the organic layer was separated from the aqueous layer, and the aqueous layer was extracted three times with ethyl acetate. The extract and the organic layer were combined and washed with saturated saline.

[0460] The extract and the organic layer were dried over magnesium sulfate. The resulting mixture was gravity filtered to remove sulfur. The magnesium salt was removed, and the filtrate was concentrated to obtain a solid. The obtained solid was then purified by silica gel column chromatography. The resulting product was purified by chromatography (eluent: hexane:toluene = 3:7). The fractions were concentrated to give the desired white solid, 2.1 g, 83% yield. The synthesis scheme of the above is shown below (E1-1).

[0461] [ka]

[0462] The results of measuring the MS spectrum of the obtained compound are shown below. MS (ESI-MS): m / z=336 (M+H) + ;C 24 H 17 NO(335.13 )

[0463] [Step 2: N,N'-bis[4-(dibenzofuran-4-yl)phenyl]-N,N Synthesis of '-diphenyl-pyrene-1,6-diamine (abbreviation: 1,6FrBAPrn-II) [How to create]

[0464] 1,6-Dibromopyrene 0.6g (1.7mmol), 4-(dibenzofuran-4-yl ) Diphenylamine 1.2g (3.4mmol), sodium tert-butoxide 0 0.5 g (5.2 mmol) was placed in a 50 mL three-neck flask, and the atmosphere inside the flask was replaced with nitrogen. Add 17.0 mL of toluene and 10% hexanediaminetetraacetate to the mixture. 0.3 mL of San solution was added.

[0465] The mixture was heated to 80° C. and 33.4 ml of bis(dibenzylideneacetone)palladium(0) was added. g (0.1 mmol) was added, and the mixture was stirred at 80°C for 4.0 hours. After stirring, The mixture was filtered through Celite and alumina with suction to obtain a filtrate. The filtrate was concentrated to obtain a solid. Ta.

[0466] The obtained solid was purified by silica gel column chromatography (eluent: hexane:toluene) The fraction was purified by elution with hexane (hexane = 7:3) and the obtained fraction was concentrated. The solid was washed with chloroform and hexane to give 1.0 g of a yellow solid in a yield of 66%.

[0467] The resulting yellow solid (1.0 g) was purified by train sublimation. The purification conditions were: pressure 2.6 Pa, argon gas flow rate 5.0 mL / min, The yellow solid was heated at 370°C. After purification by sublimation, 0.8g of yellow solid was obtained with a recovery rate of 86%. The synthetic scheme of step 2 above is shown below (E1-2).

[0468] [ka]

[0469] The compounds synthesized in the above steps were analyzed by nuclear magnetic resonance (NMR) and MS spectroscopy. N,N'-bis[4-(dibenzofuran-4-yl)phenyl]-N,N'-diphenyl Confirmed to be ruthenium-pyrene-1,6-diamine (abbreviation: 1,6FrBAPrn-II) did.

[0470] The obtained compound 1 The 1 H NMR data is shown below. 1 H NMR (CDCl3,300MHz): δ=7.02(t, J=6.9Hz, 2H ), 7.20-7.48(m, 18H), 7.56(d, J=7.8Hz, 4H), 7. 81(d, J=8.7Hz, 4H), 7.88-8.01(m, 8H), 8.17(d, J=8.4Hz, 2H), 8.23(d, J=9.3Hz, 2H)

[0471] Also, 1 The H NMR charts are shown in Figures 28(A) and (B). This is a chart showing an expanded range of 6.75 ppm to 8.50 ppm in 28(A). be.

[0472] The results of measuring the MS spectrum of the obtained compound are shown below. MS (ESI-MS): m / z=869 (M+H) + ;C 64 H 40 N2O2(868. 31)

[0473] The absorption spectrum of 1,6FrBAPrn-II in a toluene solution is shown in FIG. The emission spectrum is shown in Figure 29(B). The absorption spectrum is shown in FIG. 30(A) and the emission spectrum is shown in FIG. The spectrum and emission spectrum were measured using the same apparatus and method as in Example 1. The absorption spectra in FIG. 29(A) and FIG. 30(A) are the same as those in Example 1. The absorption spectra are shown in Figures 29 and 30 with the reference spectrum subtracted. In the figure, the horizontal axis represents wavelength (nm) and the vertical axis represents intensity (arbitrary units). In the case of a toluene solution, Absorption is observed around 433 nm, and the maximum emission wavelength is 464 nm (excitation wavelength 370 nm). In the case of the thin film, absorption was observed around 443 nm, and the maximum emission wavelength was 528 nm. (Excitation wavelength 441 nm).

[0474] From these results, the Stokes shift of 1,6FrBAPrn-II in toluene solution It was confirmed that the size was as small as 31 nm.

[0475] In addition, the HOMO and LUMO levels of 1,6FrBAPrn-II in the thin film state were measured. The measurement was carried out using the same equipment and method as in Example 1. The HOMO level of Prn-II is -5.49 eV and the energy gap is 2.6 The optical density was 2 eV, and the LUMO level was −2.87 eV.

[0476] The redox reaction characteristics were examined by CV measurement in the same manner as in Example 1.

[0477] In the CV measurement of this example, the potential of the working electrode relative to the reference electrode was changed from -0.10 V to 0 After scanning to 0.6V, the voltage was scanned from 0.6V to -0.10V, showing no oxidation. A clear peak was observed. Even after 100 cycles of scanning, the peak The shape of the 1,6FrBAPrn-II hardly changed after oxidation. It was confirmed that the compound exhibits good properties in the repeated oxidation-reduction between the neutral and neutral states. Ta.

[0478] In this CV measurement, the oxidation peak potential (from neutral to oxidation) E pa is 0.52 V. The reduction peak potential (between the oxidation side and neutral side) E pc was 0.43V. Therefore, the half-wave potential (E pa and E pc The intermediate potential, (E pa +E pc ) / 2[V]) This means that 1,6FrBAPrn-II is 0.48[V vs. Ag / Ag + ] is oxidized by the electrical energy of As mentioned above, the potential energy of the reference electrode relative to the vacuum level is -4.94 [eV], so the HOMO level of 1,6FrBAPrn-II is -4.94-0. It was confirmed that 48=-5.42[eV].

[0479] For 1,6FrBAPrn-II, the same apparatus and measurement method as in Example 1 were used to measure thermal Weight measurement and differential thermal analysis were performed. From the relationship between weight and temperature (thermogravimetry), 1,6FrBA The 5% weight loss temperature of Prn-II was over 500°C, indicating good heat resistance. EXAMPLES

[0480] In this example, a light-emitting element using the aromatic amine derivative described in Embodiment 2 as a light-emitting material was The fabrication method of the light-emitting element and the measurement results of the element characteristics are shown. N,N'-bis(dibenzofuran-4-yl)-N,N'-diphenyl ether represented by (G6-1) phenyl-pyrene-1,6-diamine (abbreviation: 1,6FrAPrn-II) was used as a light-emitting element 2 N,N'-bis(dibenzothiophene-4-yl) represented by structural formula (G6-2) -N,N'-diphenyl-pyrene-1,6-diamine (abbreviation: 1,6ThAPrn-II The light-emitting element 3 is an N,N'-bis(dibenzofuran) compound represented by the structural formula (G10-1). 1,6Fr APrn) was used as light-emitting element 4, N,N'-diphenyl-pyrene-1,6-diamine (abbreviation A light-emitting element formed using a fluorine-containing compound (1,6ThAPrn) is shown.

[0481] A method for manufacturing the light-emitting elements 1 to 4 will be described below with reference to FIG. The structural formulas of the organic compounds used are shown below.

[0482] [ka]

[0483] (Light emitting element 1) First, an anode 2102 was formed on a substrate 2101, which was a glass substrate. A 110 nm thick indium oxide-tin oxide film containing silicon oxide was formed by the etching method. The resulting membrane was processed to have an electrode area of ​​2 mm x 2 mm.

[0484] Next, an EL layer having a plurality of layers stacked on the anode 2102 was formed. The L layer is a hole injection layer 2103, a hole transport layer 2104, a light emitting layer 2105, an electron transport layer 2106, and a 6 and an electron injection layer 2107 are laminated in this order.

[0485] In this embodiment, the substrate 2101 on which the anode 2102 is formed is placed on a substrate provided in a vacuum deposition apparatus. When the substrate was fixed to the substrate holder, the surface on which the anode 2102 was formed was placed downward. The inside of the vacuum deposition device was -4 After reducing the pressure to about Pa, a hole The injection layer 2103 is 4,4'-bis[N-(1-naphthyl)-N-phenylamino] It was formed by co-evaporation of biphenyl (NPB) and molybdenum (VI) oxide. The thickness of the hole injection layer 2103 formed was 50 nm, and the ratio of NPB to molybdenum oxide (VI) was The deposition rate was adjusted so that the weight ratio was 4:1 (=NPB:molybdenum oxide). The co-evaporation method is a method in which deposition is performed simultaneously from multiple evaporation sources in one processing chamber. do.

[0486] Next, a hole transport layer having a thickness of 10 nm was formed on the hole injection layer 2103 by a deposition method using resistance heating. A layer 2104 was formed. Note that NPB was used for the hole transport layer 2104.

[0487] Next, on the hole transport layer 2104, 9-[4-(10-phenyl- 9-Anthryl)phenyl]-9H-carbazole (abbreviation: CzPA) and N,N'-bis (Dibenzofuran-4-yl)-N,N'-diphenyl-pyrene-1,6-diamine (abbreviation The light-emitting layer 2105 was formed by co-evaporation of 1,6FrAPrn-II. The thickness of the layer was 30 nm, and the weight ratio of CzPA to 1,6FrAPrn-II was 1:0.0. The deposition rate was adjusted so that the total amount of CzPA was 5 (=CzPA:1,6FrAPrn-II).

[0488] Next, tris(8-quinolinolato)aryl is deposited on the light-emitting layer 2105 by a deposition method using resistance heating. Aluminum (abbreviation: Alq) was applied to the Alq, and bathophenanthroline (abbreviation: BPhen The Alq and BPhen were used as the electron transport layer 2106. In the electron transport layer 2106, the thickness of the Alq is 10 nm and the thickness of the BPhen is It is 15nm.

[0489] Next, a lithium fluoride film having a thickness of 1 nm was formed on the electron transport layer 2106 as an electron injection layer 2107. The electron injection layer 2107 was formed by using a deposition method with resistance heating. Successful.

[0490] Finally, a cathode 2108 is formed on the electron injection layer 2107 by using a deposition method using resistance heating. The light-emitting device 1 of this example was fabricated. Aluminum was formed.

[0491] (Light emitting element 2) The light-emitting element 2 was formed in the same manner as the light-emitting element 1 except for the light-emitting layer 2105. As the light-emitting layer 2105, 9-[4-(10-phenyl-9-anthryl)phenyl] -9H-carbazole (abbreviation: CzPA) and N,N'-bis(dibenzothiophene-4- yl)-N,N'-diphenyl-pyrene-1,6-diamine (abbreviation: 1,6ThAPrn The light-emitting layer 2105 was formed to a thickness of 30 nm. The weight ratio of CzPA to 1,6ThAPrn-II was 1:0.05 (=CzPA:1,6 The deposition rate was adjusted so that the concentration of ThAPrn-II was obtained.

[0492] In this manner, the light-emitting device 2 of this example was fabricated.

[0493] (Light emitting element 3) The light-emitting element 3 was formed in the same manner as the light-emitting element 1 except for the light-emitting layer 2105. As the light-emitting layer 2105, 9-[4-(10-phenyl-9-anthryl)phenyl] -9H-carbazole (abbreviation: CzPA) and N,N'-bis(dibenzofuran-2-yl) )-N,N'-diphenyl-pyrene-1,6-diamine (abbreviation: 1,6FrAPrn) and The light-emitting layer 2105 was formed to a thickness of 30 nm by co-evaporation. The weight ratio of CzPA to 1,6FrAPrn was 1:0.01 (=CzPA:1,6FrAPrn). The deposition rate was adjusted so that

[0494] In this manner, the light-emitting device 3 of this example was fabricated.

[0495] (Light emitting element 4) The light-emitting element 4 was formed in the same manner as the light-emitting element 1 except for the light-emitting layer 2105. As the light-emitting layer 2105, 9-[4-(10-phenyl-9-anthryl)phenyl] -9H-carbazole (abbreviation: CzPA) and N,N'-bis(dibenzothiophene-2- yl)-N,N'-diphenyl-pyrene-1,6-diamine (abbreviation: 1,6ThAPrn The light-emitting layer 2105 thus formed had a thickness of 30 nm, and was made of CzP The weight ratio of A to 1,6ThAPrn was 1:0.01 (=CzPA:1,6ThAPrn The deposition rate was adjusted so that

[0496] In this manner, the light-emitting device 4 of this example was fabricated.

[0497] The element structures of the light-emitting elements 1 to 4 fabricated in this example are shown in Table 1. In Table 1, the mixture ratios are all Expressed as weight ratio.

[0498] [Table 1]

[0499] The light-emitting elements 1 to 4 thus obtained were placed in a glove box with a nitrogen atmosphere. After sealing the light-emitting element so that it is not exposed to the atmosphere, the operating characteristics of the light-emitting element were The measurements were carried out at room temperature (an atmosphere maintained at 25°C).

[0500] FIG. 32 shows voltage-luminance characteristics of the light-emitting elements 1 to 4, and FIG. 33 shows luminance-current efficiency characteristics of the light-emitting elements 1 to 4. In Figure 32, the vertical axis indicates luminance (cd / m 2 ), the horizontal axis shows voltage (V), and in Figure 33, the vertical axis The horizontal axis shows the current efficiency (cd / A), and the horizontal axis shows the brightness (cd / m 2 ) and 1000cd / m 2 The chromaticity of the light-emitting element in the vicinity is shown in Table 2.

[0501] [Table 2]

[0502] FIG. 34 shows emission spectra of the light-emitting elements 1 to 4.

[0503] From Table 2 and FIG. 34, it is confirmed that all of the light-emitting elements 1 to 4 exhibit good blue light emission. Among them, 1000cd / m 2 The y-coordinate of the chromaticity of light-emitting element 1 in the vicinity The emission spectrum peak of the light-emitting element 1 is at the shortest wavelength side, around 454 nm. From this, it was confirmed that Light-emitting Device 1 exhibited blue light with the highest color purity.

[0504] In addition, reliability tests were performed on the light-emitting elements 1 to 4. m 2 The elements are driven under a constant current density condition, and the brightness increases every time a certain period of time passes. The results of this reliability test are shown in FIG. The horizontal axis is the power-on time (hours), and the vertical axis is the ratio of brightness to the initial brightness at each time. In other words, it represents the normalized luminance (%).

[0505] As shown in FIG. 35, after 100 hours of driving, the normalized luminance of each of the light-emitting elements 1 to 4 was Since the efficiency is 80% or more, it can be said that this is a light-emitting element with a long life.

[0506] As described above, the light-emitting elements 1 to 4 of this embodiment are blue light-emitting elements having a long life and high color purity. Among them, the light-emitting element 1 is a blue light-emitting element having the highest color purity. It was confirmed that this is possible. EXAMPLES

[0507] In this example, a light-emitting element using the aromatic amine derivative described in Embodiment 3 as a light-emitting material was Specifically, the light-emitting element 5 is made of a light-emitting material and a The structural formula (G7-1) is N,N'-bis[3-(dibenzofuran-4-yl) )phenyl]-N,N'-diphenyl-pyrene-1,6-diamine (abbreviation: 1,6mFr The light-emitting element 6 is a light-emitting element using BAPrn-II as a light-emitting material. N,N'-bis[3-(dibenzothiophene-4-yl)phenyl]phenyl]propane represented by the formula (G7-2): phenyl)-N,N'-diphenyl-pyrene-1,6-diamine (abbreviation: 1,6mThBA The light-emitting element 7 is a light-emitting element using a light-emitting material having the structural formula ( G8-1) N,N'-bis[4-(dibenzofuran-4-yl)phenyl]- N,N'-diphenyl-pyrene-1,6-diamine (abbreviation: 1,6FrBAPrn-II ) is a light-emitting element.

[0508] The light-emitting element 5 and the light-emitting element 6 are configured as follows: an anode 2102, an electron transport layer 2106, an electron injection The light-emitting element 1 to the light-emitting element 2 described in Example 8 are formed in the insulating layer 2107 and the cathode 2108. The same as in Example 4, except that the light-emitting layer 2105, the hole injection layer 2103, and the hole transport layer 2104 are The element of the light-emitting element 7 is different from that of the light-emitting element 1 to the light-emitting element 4 described in Example 8. The sub-structure includes an anode 2102, a hole injection layer 2103, a hole transport layer 2104, and an electron transport layer 2105. 6, the electron injection layer 2107, and the cathode 2108 are the same as those of the light-emitting device 1 described in Example 8. The light-emitting element is the same as the light-emitting element 4, but the light-emitting layer 2105 is the light-emitting element described in Example 8. The structure of the organic compound newly used in this embodiment is shown below.

[0509] [ka]

[0510] (Light emitting element 5) An anode 2102 was formed on a substrate 2101 in the same manner as in Example 8. As the hole injection layer 2103, 9-phenyl-3-[4-(10-phenyl PCzPA and molybdenum oxide The hole injection layer 2 was formed by the co-evaporation method described in Example 8. The thickness of 103 was 50 nm, and the ratio of PCzPA to molybdenum (VI) oxide was 100% by weight. The deposition rate was adjusted to 4:2 (=PCzPA:molybdenum oxide).

[0511] Next, a hole transport layer having a thickness of 10 nm was formed on the hole injection layer 2103 by a deposition method using resistance heating. A layer 2104 was formed. Note that the hole transport layer 2104 was made of PCzPA.

[0512] In the light-emitting element 5, a light-emitting layer 2105 is formed on the hole-transporting layer 2104. 10-Phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: CzPA) and N,N'-bis[3-(dibenzofuran-4-yl)phenyl]-N,N'-diphenyl Ruthenium-1,6-diamine (abbreviation: 1,6mFrBAPrn-II) in Example 8 The light-emitting layer 2105 was formed by the co-evaporation method described above. The thickness of the formed light-emitting layer 2105 was 30 nm. The weight ratio of PA to 1,6mFrBAPrn-II was 1:0.05 (=CzPA:1,6 The deposition rate was adjusted so that the concentration of ZnO in the solution was 1.25% by weight (mFrBAPrn-II).

[0513] The electron transport layer 2106, the electron injection layer 2107, and the cathode 2108 were formed in the same manner as in Example 8. Thus, the light-emitting device 5 of this example was fabricated.

[0514] (Light emitting element 6) An anode 2102 was formed on a substrate 2101 in the same manner as in the eighth embodiment.

[0515] Next, the hole injection layer 2103 and the hole transport layer 2104 of the light-emitting element 6 are formed in the same manner as the light-emitting element 5. Next, a light-emitting layer 2105 of the light-emitting element 6 was formed by the method described above. N,N'-(9-anthryl)phenyl]-9H-carbazole (abbreviation: CzPA) and -Bis[3-(dibenzothiophen-4-yl)phenyl]-N,N'-diphenyl-pi 1,6mThBAPrn-II) and The light-emitting layer 2105 was formed to a thickness of 30 nm by co-evaporation of CzPA and The weight ratio of 1,6mThBAPrn-II was 1:0.05 (=CzPA:1,6mTh The deposition rate was adjusted so that the temperature was 100° C. (BAPrn-II).

[0516] Thereafter, the electron transport layer 2106, the electron injection layer 2107, and the cathode 2108 were formed by the same method as in Example 8. The light-emitting element 6 of this example was fabricated in the same manner as the light-emitting elements 1 to 4.

[0517] (Light emitting element 7) An anode 2102, a hole injection layer 2103, and a hole transport layer 2104 are formed on a substrate 2101. Formed as in Example 8.

[0518] Next, as the light-emitting layer 2105 of the light-emitting element 7, 9-[4-(10-phenyl-9-anthracene) N,N'-bis[4-(diphenyl)phenyl]-9H-carbazole (abbreviation: CzPA) N,N'-diphenyl-pyrene-1,6-diamine (abbreviation: 1,6FrBAPrn-II) was formed by the co-evaporation method described in Example 8. The thickness of the formed light-emitting layer 2105 was 30 nm, and it was composed of CzPA and 1,6FrBAPrn-I The weight ratio of CzPA to 1,6FrBAPrn-II was 1:0.05 (=CzPA:1,6FrBAPrn-II). The deposition rate was adjusted to

[0519] Thereafter, the electron transport layer 2106, the electron injection layer 2107, and the cathode 2108 were formed by the same method as in Example 8. The light-emitting element 7 of this example was fabricated in the same manner as the light-emitting elements 1 to 4.

[0520] The element configurations of the light-emitting elements 5 to 7 fabricated in this example are shown in Table 3. In Table 3, the mixture ratios are all Expressed as weight ratio.

[0521] [Table 3]

[0522] The light-emitting elements 5 to 7 thus obtained were placed in a glove box with a nitrogen atmosphere. After sealing the light emitting element so that it is not exposed to the atmosphere, the operating characteristics of the light emitting element are The measurements were carried out at room temperature (an atmosphere maintained at 25°C).

[0523] FIG. 36 shows voltage-luminance characteristics of the light-emitting elements 5 to 7, and FIG. 37 shows luminance-current efficiency characteristics of the light-emitting elements 5 to 7. In Fig. 36, the vertical axis indicates luminance (cd / m 2 ), the horizontal axis shows voltage (V), and in Figure 37 The vertical axis represents current efficiency (cd / A) and the horizontal axis represents luminance (cd / m 2 ) is also shown. d / m 2 The chromaticity of the light-emitting element in the vicinity is shown in Table 4.

[0524] [Table 4]

[0525] FIG. 38 shows the emission spectra of the light-emitting elements 5 to 7.

[0526] No significant difference in luminance with respect to voltage was observed in any of the light-emitting elements 5 to 7. 4 and, from FIG. 38, it can be seen that the light-emitting elements 5 to 7 all exhibit good blue light emission. It was confirmed that the light-emitting elements 5 and 6 had a higher emission spectrum peak than the light-emitting element 7. Since this appears on the short wavelength side, around 460 nm, it can be said to exhibit a blue color with high color purity.

[0527] In addition, reliability tests were performed on the light-emitting elements 5 to 7. 0 cd / m 2 The elements are driven under a constant current density condition, and after a certain period of time The luminance was measured every time the light was turned on. The results of the reliability test are shown in Figure 39. The horizontal axis is the time of current application (hours), and the vertical axis is the luminance at each time relative to the initial luminance. This represents the percentage of normalized brightness (%).

[0528] As shown in FIG. 39, after 100 hours of driving, the light-emitting elements 5 to 7 all had the same It was confirmed that the rated luminance was 90% or more, and that the device was a long-life light-emitting device.

[0529] As described above, the light-emitting elements 5 to 7 of this embodiment emit blue light with a long life and high color purity. It was confirmed that it is possible to use the resulting material as a light-emitting element. [Explanation of symbols]

[0530] 101 Substrate 102 electrode 103 EL layer 104 Electrode 111 First layer (hole injection layer) 112 Second layer (hole transport layer) 113 Third layer (light-emitting layer) 114 4th layer (electron transport layer) 115 5th layer (electron injection layer) 311 First Light Emitting Unit 312 Second Light Emitting Unit 313 Charge generation layer 321 First electrode 322 Second electrode 401 Source side drive circuit 402 Pixel section 403 Gate side drive circuit 404 Sealing substrate 405 Sealing material 407 Space 408 Wiring 409 FPC (Flexible Printed Circuit) 410 Element substrate 411 Switching TFT 412 Current Control TFT 413 Electrode 414 Insulation 416 EL layer 417 Electrode 418 Light-emitting element 423 N-channel TFT 424 P-channel TFT 501 Substrate 502 Electrode 503 Electrode 504 EL layer 505 Insulation Layer 506 Partition layer 611 Case 612 Support stand 613 Display section 614 Speaker section 615 Video input terminal 621 Main unit 622 Case 623 Display section 624 Keyboard 625 External connection port 626 Pointing Device 631 Main unit 632 Case 633 Display section 634 Audio input section 635 Audio output section 636 Operation Key 637 External connection port 638 Antenna 641 Main unit 642 Display section 643 Case 644 External connection port 645 Remote control receiver 646 Image receiving unit 647 Battery 648 Audio Input Unit 649 Operation Key 650 Eyepiece 700 Table Lamp 701 Lighting Equipment 2101 Substrate 2102 Anode 2103 Hole injection layer 2104 Hole transport layer 2105 Light-emitting layer 2106 Electron transport layer 2107 Electron injection layer 2108 Cathode

Claims

1. An aromatic amine derivative represented by the formula (G1): 【Chemistry 1】 (Wherein, A represents oxygen or sulfur, R １ ~R ７ R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group. １ ~R ７ represents an alkyl group having 1 to 6 carbon atoms. １ and α ２ Each of Ar independently represents a substituted or unsubstituted phenylene group. １ represents any one of substituted or unsubstituted pyrene, substituted or unsubstituted anthracene, substituted or unsubstituted chrysene, and substituted or unsubstituted tetracene. ２ represents a substituted or unsubstituted aryl group having 6 to 13 carbon atoms forming a ring; j is 0 or 1, n is 0 or 1, and p is 1 or 2.

2. In claim 1, Ar in formula (G1) １ The aromatic amine derivative is represented by the following formula (Ar1-1) or (Ar1-2): 【Chemistry 2】 (In formulas (Ar1-1) and (Ar1-2), R ８ ~R １０ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group. However, in the case of (Ar1-1), p in formula (G1) is 1, and in the case of (Ar1-2), p is 2.

3. In claim 1 or 2, Ar ２ The aromatic amine derivative is represented by any one of the following formulae (Ar2-1) to (Ar2-6). 【Chemistry 3】

4. In any one of claims 1 to 3, R １ ~R １０ each independently represents any one of aromatic amine derivatives represented by the following formulas (R-1) to (R-6), (R-8), and (R-9). 【Chemistry 4】

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