JPH11273864A - Organic electroluminescence device - Google Patents

Abstract

(57) [Problem] To provide a group of organic EL elements having high luminous efficiency and various luminescent colors. SOLUTION: The organic electroluminescence device contains, as a light emitting material, at least one selected from the group consisting of a specific anthracene derivative, a bianthryl derivative, a perylene derivative and a tetracene derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescence (EL) device and an organic EL display using the same. Organic EL elements have characteristics such as self-luminous emission and high-speed response, and are expected to be applied to flat panel displays (Ref: Nikkei Electronics, 1
996.1.29, p99).

[0002]

2. Description of the Related Art In an organic EL device, it is necessary that the ratio of the amount of light emitted to the amount of current injected into the device (luminous efficiency) is large. The luminous efficiency of an organic EL device is proportional to the fluorescence quantum yield of a luminescent material molecule contained in the device. The luminous efficiency of the device was low because the fluorescent quantum yield of the luminescent molecule used in the conventional organic EL device was not sufficient.

[0003] Further, in the case where an organic EL element is formed into a display, an organic EL element having various luminescent colors is required.
Since the emission color of the organic EL element is determined by the intrinsic excitation energy of the light emitting molecule, it is necessary to prepare another kind of light emitting molecule.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic EL device using a molecule having a large fluorescence quantum yield to provide an organic EL device having a high luminous efficiency. The present invention also provides a group of organic EL elements each having a large fluorescence quantum yield and using a group of molecules having different excitation energies to form organic EL elements, and having high luminous efficiency and various luminescent colors. What you want to do.

[0005]

According to the present invention, as a light-emitting material, the following formulas 1, 2, 3, 4,
5, 6 and 7

[0006]

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(Wherein R ₁ represents H or —CN)

[0008]

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(In the above formula, R_TwoAnd R_ThreeIs Al
Represents a kill group;_FourIs H or -NR _TwoR_ThreeRepresents)

[0010]

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(Wherein R ₅ represents an alkyl group)

[0012]

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(Wherein R ₆ is H, F, Cl, -CN,
Represents an alkyl group or an aryl group)

[0014]

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[0015] (In the formula, R ₇ represents an alkyl group, R ₈
Is H, F, Cl, an alkyl group, an aryl group or -OR
₇ )

[0016]

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(Wherein R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each represent H or —CN, provided that R ₉ , R ₁₀ ,
At least one of R ₁₁ and R ₁₂ is -CN

[0018]

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(Wherein, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ each represent H or —CN, provided that R ₁₃ , R ₁₄ ,
At least one of R ₁₅ and R ₁₆ is —CN), and an organic EL device including at least one selected from the group consisting of an anthracene derivative, a bianthryl derivative, a perylene derivative, and a tetracene derivative. .

The organic EL device of the present invention further comprises the following formula 8

[0021]

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9,9'-bianthryl represented by the formula: The present invention also provides an organic EL display including the above-mentioned organic EL element.

[0023]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The organic EL device of the present invention typically comprises an anode electrode 2, a hole transport layer 3, and a light emitting layer 4, which are sequentially provided on a substrate 1, as shown in FIG. , Electron transport layer 5
And the cathode electrode 6, but the electron transport layer 5 may not be provided. Examples of the substrate material include glass such as soda lime glass and borosilicate glass, and synthetic resins such as polycarbonate, acrylic, and epoxy.

As the anode electrode, SnO ₂ , In
A transparent electrode such as O ₂ or ITO, a translucent electrode made of gold or nickel, or the like can be used. Further, as a cathode electrode material, Mg, Al, Ag, In, Li, Na
It is preferable to use a metal that can be formed to a thickness of 30 nm or more by a vacuum evaporation method or a sputtering method.

As a material for the hole transport layer, a compound represented by the following formula can be used.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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Further, as a material for the electron transport layer, a compound represented by the following formula can be used.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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In the present invention, when the 9,9'-bianthryl of the formula 8 is used together with the anthracene derivative, the bianthryl derivative, the perylene derivative or the tetracene derivative of the formulas 1 to 7 as described above, the molecule existing in the light emitting layer It is preferred to use 9,9'-bianthryl in such an amount that the number of molecules of the derivatives of the formulas 1 to 7 is 0.01 to 80%, especially 0.1 to 20%, based on the total number of It has been found that when 9,9'-bianthryl is used as a material for the light emitting layer, the film quality of the light emitting layer can be improved and light emission with high efficiency can be obtained.

The organic EL device of the present invention has the advantage that it exhibits high efficiency and can obtain a variety of luminescent colors by appropriately selecting the luminescent molecules. Can be configured.

[0048]

The present invention will be further described below with reference to examples and comparative examples. Example 1 Using a solution of anthracene in methylcyclohexane as a standard substance for fluorescence quantum yield (fluorescence quantum yield 0.31), literature (Yasuharu Nishikawa, Keizo Hiraki, "Fluorescence and phosphorescence analysis",
According to the method of Kyoritsu Shuppan, 1984, pp. 76-80, the fluorescence quantum yield of 9-cyanoanthracene (the compound in which R ₁ is H in Formula 1) was measured. Anthracene and 9-cyanoanthracene were measured in a 3 × 10 ⁻⁷ M methylcyclohexane solution, and replaced with nitrogen to eliminate the influence of oxygen. The fluorescence quantum yield of 9-cyanoanthracene was 0.98. Example 2 In the same manner as in Example 1, the fluorescence quantum yield of 9,10-dicyanoanthracene (a compound in which R ₁ is —CN in Formula 1) was measured. The fluorescence quantum yield was 1.0. Comparative Example 1 In the same manner as in Example 1, the fluorescence quantum yield of 1-cyanoanthracene represented by the following formula was measured. The fluorescence quantum yield was 0.24.

[0049]

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Comparative Example 2 The fluorescence quantum yield of 2-cyanoanthracene (following formula) was measured in the same manner as in Example 1, and a fluorescence quantum yield of 0.35 was obtained.

[0051]

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Comparative Example 3 The fluorescence quantum yield of 1,4-dicyanoanthracene (following formula) was measured in the same manner as in Example 1, and a fluorescence quantum yield of 0.53 was obtained.

[0053]

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Comparative Example 4 The fluorescence quantum yield of 1,5-dicyanoanthracene (following formula) was measured in the same manner as in Example 1, and a fluorescence quantum yield of 0.38 was obtained.

[0055]

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Example 3 A laminated organic EL device having the structure shown in FIG. 1 was manufactured using 9-cyanoanthracene as follows. ITO electrode 2
The glass substrate 1 is washed with water, acetone, and isopropyl alcohol, and is vacuum-evaporated (1 × 10 ⁻⁶ torr).
r, substrate temperature is room temperature), and a hole transport layer 3
As TPD (the following formula)

[0057]

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Is 50 nm, 9-cyanoanthracene is 10 nm as the light emitting layer 4 thereon, and t-Bu-PBD is formed thereon as the electron transporting layer 5 (the following formula).

[0059]

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Of 50 nm, and an Al-Li alloy
6 (Li: 0.5% by weight) was deposited to a thickness of 50 nm. This element
A voltage is applied with ITO as the positive electrode and Al-Li as the negative electrode
Then, blue light emission was observed at a voltage of 3 V or more, and the applied voltage
Emission luminance of 1250 cd / m at 10 V^TwoIs observed
Was. Example 4 Using 9,10-dicyanoanthracene as follows
A stacked organic EL device having the structure shown in FIG. 1 was produced. IT
Water, acetone, isopropyl
After washing with alcohol, vacuum evaporation equipment (1 × 10^-6
(torr, substrate temperature is room temperature).
TPD of 50 nm as the transmitting layer 3 and the light emitting layer 4 thereon
9,10-dicyanoanthracene has a thickness of 10 nm, and
T-Bu-PBD of 50 nm as the
Al-Li alloy 6 (Li: 0.5% by weight)
nm deposited. This device has ITO as a positive electrode and Al-Li as a
When a voltage is applied as a negative electrode, blue light is emitted at a voltage of 3 V or more.
Was observed, and the emission luminance was 1460 at an applied voltage of 10 V.
cd / m^TwoWas observed. Comparative Example 5 As shown in FIG. 1 using 1-cyanoanthracene as follows.
A stacked organic EL device having a structure shown in FIG. ITO electrode 2
Glass substrate 1 with water, acetone, isopropyl alcohol
Cleaning with a vacuum tool and a vacuum deposition device (1 × 10^-6tor
r, substrate temperature is room temperature), and a hole transport layer 3
As a light emitting layer 4 on top of 50 nm TPD.
Ananothracene having a thickness of 10 nm and an electron transport layer 5 thereon
T-Bu-PBD to 50 nm, and furthermore, Al-L
i-alloy 6 (Li: 0.5% by weight) was deposited to a thickness of 50 nm. This
The voltage of the device with ITO as the positive electrode and Al-Li as the negative electrode
When light is applied, no light emission is observed up to a voltage of 5 V.
The emission luminance at a pressure of 10 V is 150 cd / m.^TwoMet. COMPARATIVE EXAMPLE 6 A diagram using 1,5-dicyanoanthracene as follows:
A stacked organic EL device having the structure shown in FIG. ITO
Water, acetone, isopropyl
After washing with alcohol, a vacuum evaporation device (1 × 10^-6t
orr, substrate temperature is room temperature), and hole transport
TPD of 50 nm as the layer 3 and the light emitting layer 4 thereon
1,5-dicyanoanthracene is 10 nm, and electron
50 nm of PBD as a transport layer 5 and furthermore Al-
Li alloy 6 (Li: 0.5% by weight) was deposited to a thickness of 50 nm.
This element is charged with ITO as the positive electrode and Al-Li as the negative electrode.
When pressure is applied, no light emission is observed up to a voltage of 5 V.
Emission luminance at a voltage of 10 V is 180 cd / m.^TwoSo
Was. Example 5 9-cyanoanthracene and 9,9'-via as follows
1. A stacked organic EL device having a structure shown in FIG.
Was prepared. Glass substrate 1 with ITO electrode 2
Washed with isopropyl alcohol and vacuum deposited
Equipment (1 × 10 ^-6torr, substrate temperature is room temperature)
On top of this, 50 nm of TPD was
9-cyanoanthracene and 9,9 ′
-Layer with simultaneous deposition of Viantril (deposition ratio 9-cyanoa
9,9'-bianthryl 9 min per molecule of anthracene
) Is 10 nm, and t-Bu-
PBD is 50 nm, and an Al-Li alloy 6 (L
i: 0.5% by weight). This element has I
Applying voltage with TO as the positive electrode and Al-Li as the negative electrode
And blue light emission was observed at a voltage of 3 V or more, and an applied voltage of 10
Emission luminance at 1850 cd / m^TwoWas observed. Example 6 9,10-dicyanoanthracene and 9,
Using 9'-bianthryl, a laminated type having the structure shown in FIG.
An EL device was manufactured. Glass substrate 1 with ITO electrode 2
Is washed with water, acetone and isopropyl alcohol
And a vacuum deposition device (1 × 10^-6Torr, substrate temperature is room
Temperature) to form a hole transport layer 3 on top of TPD
0 nm, and 9,10-dicyanoan as a light emitting layer 4 thereon
Co-deposited layer of Toracene and 9,9'-Bianthril
(Deposition ratio 9,10-dicyanoanthracene per molecule
9,9'-bianthryl (9 molecules) is 10 nm.
T-Bu-PBD of 50 nm as the
Al-Li alloy 6 (Li: 0.5% by weight)
nm deposited. This device has ITO as a positive electrode and Al-Li as a
When a voltage is applied as a negative electrode, blue light is emitted at a voltage of 3 V or more.
Is observed, and the emission luminance 2010 at an applied voltage of 10 V
cd / m^TwoWas observed. Example 7 A solution of anthracene in methylcyclohexane was subjected to fluorescence quantum harvesting.
Rate standard material (fluorescence quantum yield 0.31)
Tribute (Yasuharu Nishikawa, Keizo Hiraki, "Fluorescence and phosphorescence analysis"
Kyoritsu Shuppan, 1984, pp. 76-80)
9-dimethylaminoanthracene (in the formula 2, R
_TwoAnd R_ThreeIs methyl and R_FourIs H)
Was measured for the fluorescence quantum yield. Anthracene and 9
3 × 10 for dimethylaminoanthracene^-7M methyl
Prepare a cyclohexane solution and place in nitrogen to eliminate the effect of oxygen
The measurement was performed instead. 9-dimethylaminoanthracene
Had a fluorescence quantum yield of 0.95. Example 8 In the same manner as in Example 7, 9,10-bisdimethylamino
Anthracene (R in Formula 2_TwoAnd R_ThreeIs methyl
Yes, R_FourIs -NR_TwoR_ThreeQuantum yield of the compound
Was measured, and a fluorescence quantum yield of 0.99 was obtained.
Was. Comparative Example 7 1-dimethylaminoanthracene was prepared in the same manner as in Example 7.
Measurement of the fluorescence quantum yield of
0.20 was obtained.

[0061]

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Comparative Example 8 The fluorescence quantum yield of 2-dimethylaminoanthracene was measured in the same manner as in Example 7, and a fluorescence quantum yield of 0.26 was obtained.

[0063]

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Comparative Example 9 The fluorescence quantum yield of 1,4-bisdimethylaminoanthracene was measured in the same manner as in Example 7, and a fluorescence quantum yield of 0.40 was obtained.

[0065]

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Comparative Example 10 The fluorescence quantum yield of 1,5-bisdimethylaminoanthracene was measured in the same manner as in Example 7, and a fluorescence quantum yield of 0.28 was obtained.

[0067]

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Example 9 A laminated organic EL device having the structure shown in FIG. 1 was produced using 9-dimethylaminoanthracene as follows. IT
The glass substrate 1 with the O electrode 2 is washed with water, acetone, and isopropyl alcohol, and is then vacuum-evaporated (1 × 10 ^−6).
torr, the substrate temperature is room temperature), TPD of 50 nm as the hole transport layer 3 thereon, 9-dimethylaminoanthracene of 10 nm as the light emitting layer 4 thereon, and t-Bu as the electron transport layer 5 thereon. 50 nm of PBD, and 50 nm of Al-Li alloy 6 (Li: 0.5% by weight) thereon.
nm deposited. When a voltage was applied to this device using ITO as a positive electrode and Al-Li as a negative electrode, blue light emission was observed at a voltage of 3 V or more, and a light emission luminance of 1380 at an applied voltage of 10 V.
cd / m ² was observed. Example 10 A laminated organic EL device having the structure shown in FIG. 1 was manufactured using 9,10-bisdimethylaminoanthracene as follows. A glass substrate 1 with an ITO electrode 2 was washed with water, acetone,
After washing with isopropyl alcohol, using a vacuum deposition apparatus (1 × 10 ⁻⁶ torr, the substrate temperature is room temperature), TPD of 50 nm is formed thereon as the hole transport layer 3, and 9,10− is formed thereon as the light emitting layer 4. Bisdimethylaminoanthracene is 10 nm, on which t-Bu-P is formed as an electron transport layer 5.
BD is 50 nm, and further, Al-Li alloy 6 (L
i: 0.5% by weight). This element has I
When a voltage was applied with TO as the positive electrode and Al-Li as the negative electrode, blue light emission was observed at a voltage of 3 V or more.
At V, an emission luminance of 1490 cd / m ² was observed. Comparative Example 11 A stacked organic EL device having the structure shown in FIG. 1 was produced using 1-dimethylaminoanthracene as follows. IT
The glass substrate 1 with the O electrode 2 is washed with water, acetone, and isopropyl alcohol, and is then vacuum-evaporated (1 × 10 ^−6).
torr, the substrate temperature is room temperature), TPD of 50 nm as a hole transport layer 3 thereon, 1-dimethylaminoanthracene of 10 nm as a light emitting layer 4 thereon, and t-Bu as an electron transport layer 5 thereon. 50 nm of PBD, and 50 nm of Al-Li alloy 6 (Li: 0.5% by weight) thereon.
nm deposited. When a voltage was applied to this element using ITO as a positive electrode and Al-Li as a negative electrode, no light emission was observed up to a voltage of 6 V, and the light emission luminance at an applied voltage of 10 V was 90 cd / m 2.
^{Was 2} . Comparative Example 12 A stacked organic EL device having the structure shown in FIG. 1 was produced using 1,5-bisdimethylaminoanthracene as follows. The glass substrate 1 with the ITO electrode 2 is washed with water, acetone, and isopropyl alcohol, and
(× 10 ⁻⁶ torr, substrate temperature is room temperature). TPD is 50 nm as the hole transport layer 3 thereon, and 1,5-bisdimethylaminoanthracene is 1 as the light emitting layer 4 thereon.
0 nm, 50 nm of t-Bu-PBD as an electron transport layer 5 thereon, and an Al-Li alloy 6 (Li: 0.
5% by weight) was deposited to a thickness of 50 nm. When a voltage is applied to this device using ITO as a positive electrode and Al-Li as a negative electrode, a voltage of 5
No light emission was observed up to V, and the light emission luminance at an applied voltage of 10 V was 140 cd / m ² . Example 11 9-dimethylaminoanthracene and 9,
A laminated organic EL device having the structure shown in FIG. 1 was manufactured using 9′-bianthritol. Glass substrate 1 with ITO electrode 2
Was washed with water, acetone and isopropyl alcohol, and TPD was deposited thereon as a hole transport layer 3 using a vacuum evaporation apparatus (1 × 10 ⁻⁶ torr, substrate temperature at room temperature).
0 nm, and a layer in which 9-dimethylaminoanthracene and 9,9′-bianthryl were simultaneously vapor-deposited as a light-emitting layer 4 (a vapor deposition ratio of 9-dimethylaminoanthracene to 9 molecules of 9,9′-bianthryl) was 10 nm. On top of this, 50 nm of t-Bu-PBD is used as an electron transport layer 5, and 50 nm of Al-Li alloy 6 (Li: 0.5% by weight) is further added thereon.
nm deposited. When a voltage was applied to this element using ITO as a positive electrode and Al-Li as a negative electrode, blue light emission was observed at a voltage of 3 V or more, and a light emission luminance of 1720 at an applied voltage of 10 V.
cd / m ² was observed. Example 12 A laminated organic EL device having the structure shown in FIG. 1 was produced using 9,10-bisdimethylaminoanthracene and 9,9′-bianthryl as follows. The glass substrate 1 with the ITO electrode 2 is washed with water, acetone and isopropyl alcohol, and a TP is formed thereon as a hole transport layer 3 using a vacuum evaporation apparatus (1 × 10 ⁻⁶ torr, substrate temperature is room temperature).
D is 50 nm, and a layer in which 9,10-bisdimethylaminoanthracene and 9,9′-bianthryl are co-evaporated as a light-emitting layer 4 (evaporation ratio: 9,9 ′ per 9,10-bisdimethylaminoanthracene molecule) (Nine molecules of Vianthryl) of 10 nm, on which t-Bu-
PBD is 50 nm, and an Al-Li alloy 6 (L
i: 0.5% by weight). This element has I
When a voltage was applied with TO as the positive electrode and Al-Li as the negative electrode, blue light emission was observed at a voltage of 3 V or more.
At V, an emission luminance of 1870 cd / m ² was observed. Examples 13 and 14 A methylcyclohexane solution of anthracene was used as a standard substance for fluorescence quantum yield (fluorescence quantum yield 0.31), and a literature (Yasuharu Nishikawa, Keizo Hiraki, "Fluorescence and Phosphorescence Analysis",
According to the method of Kyoritsu Shuppan, 1984, pp. 76-80, 9,10-dimethoxyanthracene (Example 13,
A compound in which R ₅ is methyl in the formula 3) and 9.1
The fluorescence quantum yield of 0-diethoxyanthracene (Example 14, a compound in which R ₅ in Formula 3 is ethyl) was measured. The molecule of anthracene and the example is 3 × 10 ^-7
M was prepared as a methylcyclohexane solution, and the measurement was carried out by substituting with nitrogen to remove the influence of oxygen. Comparative Examples 13 and 14 The fluorescence quantum yields of 9-methoxyanthracene (Comparative Example 13) and 1,4-dimethoxyanthracene (Comparative Example 14) were measured in the same manner as in Example 13.

[0069]

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[0070]

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The results were as follows. Examples 15 and 16 A laminated organic EL device having the structure shown in FIG. 1 was produced using 9,10-dimethoxyanthracene (Example 15) and 9,10-diethoxyanthracene (Example 16) as follows. . The glass substrate 1 with the ITO electrode 2 is washed with water, acetone, and isopropyl alcohol, and TPD is formed thereon as a hole transport layer 3 by using a vacuum deposition apparatus (1 × 10 ⁻⁶ torr, the substrate temperature is room temperature). 9,10-dimethoxyanthracene or 9,10-diethoxyanthracene as a light emitting layer 4 thereon, 10 nm, and t-Bu-PBD as an electron transport layer 5 thereon, 50 nm.
Further, an Al-Li alloy 6 (Li: 0.5% by weight) was deposited thereon to a thickness of 50 nm. A positive electrode of ITO, A
A voltage was applied using l-Li as a negative electrode, and the light emission luminance at a light emission start voltage and an applied voltage of 10 V was observed. Comparative Examples 15 and 16 9-methoxyanthracene as follows (Comparative Example 15)
And 1,4-dimethoxyanthracene (Comparative Example 16)
Was used to produce a laminated organic EL device having the structure shown in FIG. The glass substrate 1 with the ITO electrode 2 is washed with water, acetone, and isopropyl alcohol, and
(× 10 ⁻⁶ torr, substrate temperature is room temperature), and TPD is 50 nm as the hole transport layer 3 thereon, and 9-methoxyanthracene or 1,4-dimethoxyanthracene is 10 nm as the light emitting layer 4 thereon. A 50 nm t-Bu-PBD as an electron transport layer 5 was formed thereon, and an Al-
Li alloy 6 (Li: 0.5% by weight) was deposited to a thickness of 50 nm.
A voltage was applied to this device using ITO as a positive electrode and Al-Li as a negative electrode, and the light emission starting voltage and the light emission luminance at an applied voltage of 10 V were observed. Examples 17 and 18 Lamination of the structure shown in Figure 1 using 9,10-dimethoxyanthracene (Example 17) or 9,10-diethoxyanthracene (Example 18) and 9,9'-bianthryl as follows: An organic EL device was fabricated. ITO electrode 2
The glass substrate 1 is washed with water, acetone, and isopropyl alcohol, and is vacuum-evaporated (1 × 10 ⁻⁶ torr).
r, substrate temperature is room temperature), and a hole transport layer 3
And a light emitting layer 4 of 9.1,
A layer obtained by co-evaporation of 0-dimethoxyanthracene or 9,10-diethoxyanthracene and 9,9'-bianthryl (deposition ratio; 9 molecules of 9,9'-bianthryl per molecule of each molecule in each example) is 10 nm, and T-Bu-PBD as the electron transporting layer 5 is 50 nm, and furthermore, Al-
Li alloy 6 (Li: 0.5% by weight) was deposited to a thickness of 50 nm.
A voltage was applied to this device using ITO as a positive electrode and Al-Li as a negative electrode, and the light emission starting voltage and the light emission luminance at an applied voltage of 10 V were observed. Comparative Examples 17 and 19 FIG. 1 shows anthracene (Comparative Example 17), 9-methoxyanthracene (Comparative Example 18), 1,4-dimethoxyanthracene (Comparative Example 19) and 9,9′-bianthryl as follows. A laminated organic EL device having the structure shown was produced. The glass substrate 1 with the ITO electrode 2 is washed with water, acetone, and isopropyl alcohol, and
(× 10 ⁻⁶ torr, substrate temperature is room temperature). TPD of 50 nm is formed thereon as the hole transport layer 3, and anthracene, 9-methoxyanthracene or 1,4-dimethoxyanthracene is formed thereon as the light emitting layer 4. , 9′-Bianthryl was simultaneously vapor-deposited (deposition ratio; 9 molecules of 9,9′-bianthryl per molecule of each example molecule) was 10 nm, and t-Bu-PBD was 50 nm as electron transport layer 5 thereon. Further, an Al-Li alloy 6 (Li: 0.5% by weight) is further formed thereon.
Was deposited to a thickness of 50 nm. This device has ITO as a positive electrode, Al-
A voltage was applied using Li as a negative electrode, and the light emission luminance at a light emission start voltage and an applied voltage of 10 V was observed. The results are shown below.

Emission starting voltage (V) Emission luminance (cd / m^Two, at 10 V) Example 15 3 1320 Example 16 3 1290 Example 17 3 1530 Example 18 3 1500 Comparative Example 15 5 350 Comparative Example 16 5 240 Comparative Example 17 6 180 Comparative Example 18 5 410 Comparative Example 19 4 370 Example Examples 19 to 22 Fluorescent quantum yield of anthracene in methylcyclohexane
Rate standard material (fluorescence quantum yield 0.31)
Tribute (Yasuharu Nishikawa, Keizo Hiraki, "Fluorescence and phosphorescence analysis"
Kyoritsu Shuppan, 1984, pp. 76-80)
10-cyano-9,9'-bianthryl (Example 1
9. In the formula 4, R₆Is H), 10, 1
0'-dicyano-9,9'-bianthryl (Example 2
0, R in Formula 4₆Is -CN), 10-
Methoxy-9,9'-bianthryl (Example 21, Formula 5
At R₇Is methyl and R₈Is H
Product) 10,10'-dimethoxy-9,9'-biant
Lil (Example 22, R in Formula 5) ₇Is methyl,
R₈Is -OR₇Of the fluorescence quantum yield of the compound
Was done. The molecule of anthracene and the example is 3 × 10
^-7M in methylcyclohexane to eliminate the effects of oxygen
The measurement was performed after replacing with nitrogen. Comparative Examples 20 and 21 In the same manner as in Example 19, 9,9'-bianthritol (ratio
Comparative Example 20) and 10-chloro-9,9'-biantri
Of the fluorescence quantum yield of the compound (following formula, Comparative Example 21)
Was.

[0073]

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The results are shown below. Examples 23-26 10-cyano-9,9'-bianthryl (Example 23) as follows: 10,10'-dicyano-9,9'-.
Bianthril (Example 24), 10-methoxy-9,
9'-Bianthril (Example 25) and 10,10 '
-Dimethoxy-9,9'-bianthryl (Example 26)
Was used to produce a laminated organic EL device having the structure shown in FIG. The glass substrate 1 with the ITO electrode 2 is washed with water, acetone, and isopropyl alcohol, and
(× 10 ⁻⁶ torr, the substrate temperature is room temperature), TPD of 50 nm is formed thereon as the hole transport layer 3, and 10-cyano-9,9′-bianthryl is formed thereon as the light emitting layer 4.
0,10'-dicyano-9,9'-bianthryl, 10
-Methoxy-9,9'-bianthryl or 10,1
0'-dimethoxy-9,9'-bianthryl at 10 nm,
On top of this, 50 n of t-Bu-PBD is used as an electron transport layer 5.
m, and an Al—Li alloy 6 (Li: 0.5% by weight) was further deposited thereon by 50 nm. This device has ITO as a positive electrode,
A voltage was applied using Al-Li as a negative electrode, and the emission luminance at a light emission start voltage and an applied voltage of 10 V was observed. Comparative Examples 22 and 23 9,9'-bianthryl (Comparative Example 22) and 10-chloro-9,9'-bianthryl (Comparative Example 2)
Using 3), a stacked organic EL device having the structure shown in FIG. 1 was produced. The glass substrate 1 with the ITO electrode 2 is washed with water, acetone, and isopropyl alcohol, and is then vacuum-evaporated (1 × 10 ⁻⁶ torr, substrate temperature is room temperature).
On this, TPD is 50 nm as the hole transport layer 3, and 9,9′-bianthryl or 10-chloro-9,9′-bianthryl is 10 nm as the light-emitting layer 4 thereon, and t− is formed thereon as the electron transport layer 5. Bu-PBD is 50 nm, and Al-Li alloy 6 (Li: 0.5% by weight) is further deposited thereon to 50 nm.
Evaporated. A voltage was applied to this device with ITO as the positive electrode and Al-Li as the negative electrode, and the light emission starting voltage and the applied voltage 1
The emission luminance at 0 V was observed. Examples 27-30 10-cyano-9,9'-bianthryl (Example 27) as follows: 10,10'-dicyano-9,9'-.
Bianthril (Example 28), 10-methoxy-9,
9'-bianthryl (Example 29) or 10,10 '
-Dimethoxy-9,9'-bianthryl (Example 30)
Then, a stacked organic EL device having the structure shown in FIG. The glass substrate 1 with the ITO electrode 2 is washed with water, acetone, and isopropyl alcohol, and a TPD as a hole transport layer 3 is formed thereon using a vacuum evaporation apparatus (1 × 10 ⁻⁶ torr, substrate temperature is room temperature).
Is 50 nm, and 10-cyano-9,
9-bianthryl, 10,10'-dicyano-9,9 '
-Bianthril, 10-methoxy-9,9'-bianthryl or a layer in which 10,10'-dimethoxy-9,9'-bianthryl and 9,9'-bianthryl were co-deposited (deposition ratio; one molecule in each molecule in each example) On the other hand, 9,9'-bianthryl (9 molecules) is 10 nm, on which t-Bu-PBD is 50 nm as the electron transporting layer 5, and Al-Li is further formed thereon.
Alloy 6 (Li: 0.5% by weight) was deposited to a thickness of 50 nm. A voltage was applied to this device using ITO as a positive electrode and Al-Li as a negative electrode, and the light emission starting voltage and the light emission luminance at an applied voltage of 10 V were observed. Comparative Example 24 A stacked organic EL device having the structure shown in FIG. 1 was produced using 10-chloro-9,9′-bianthryl and 9,9′-bianthryl as follows. The glass substrate 1 with the ITO electrode 2 is washed with water, acetone, and isopropyl alcohol, and TPD is formed thereon as a hole transport layer 3 by using a vacuum deposition apparatus (1 × 10 ⁻⁶ torr, the substrate temperature is room temperature). And 10-chloro-9,
One layer of 9′-bianthryl and 9,9′-bianthryl was co-evaporated (evaporation ratio: 9 molecules of 9,9′-bianthryl per molecule of 10-chloro-9,9′-bianthryl).
0 nm, 50 nm of t-Bu-PBD as an electron transport layer 5 thereon, and an Al-Li alloy 6 (Li: 0.
5% by weight) was deposited to a thickness of 50 nm. A voltage was applied to this device using ITO as a positive electrode and Al-Li as a negative electrode, and the light emission starting voltage and the light emission luminance at an applied voltage of 10 V were observed.

The results are shown below. Emission start voltage (V) Emission luminance (cd / m ² , at 10 V) Example 23 3 1470 Example 24 3 1550 Example 25 3 1420 Example 26 3 1440 Example 27 3 1620 Example 28 3 1850 Example 29 3 1580 Example 30 3 1550 Comparative Example 22 6 190 Comparative Example 23 5 370 Comparative Example 24 4 550 Examples 31 to 36 A methylcyclohexane solution of anthracene was used as a fluorescent quantum yield standard substance (fluorescent quantum yield 0.31). References (Yasuharu Nishikawa, Keizo Hiraki, "Fluorescence and Phosphorescence Analysis",
According to the method of Kyoritsu Shuppan, 1984, pp. 76-80, 3-cyanoperylene (Example 31, R in formula 6)
₉ = CN, R ₁₀ = R ₁₁ = R ₁₂ = H), 3,9-
Dicyanoperylene (Example 32, where R ₉ = R
₁₂ = CN, R ₁₀ = R ₁₁ = H), 3,4,9,1
0-tetracyanoperylene (Example 33, a compound in which R ₉ ＝ R ₁₀ ＲR ₁₁ ＲR ₁₂ ＣＮCN in formula 6), 5-cyanotetracene (Example 34, R ₁₃ ＣＮCN in formula 7, R ₁₃ = CN, R
₁₄ = R ₁₅ = R ₁₆ = H), 5,12-dicyanotetracene (Example 35, R ₁₃ = R ₁₅ = C in formula 7)
N, compounds of _{R 14 = R 16 = H)} , 5,6,11,12-
Tetracyanotetracene (Example 36;
₁₃ = R ₁₄ = R ₁₅ = R ₁₆ = CN)). The anthracene and the molecules of the examples were measured in a 3 × 10 ⁻⁷ M methylcyclohexane solution, and replaced with nitrogen to eliminate the influence of oxygen. Comparative Examples 25 to 28 In the same manner as in Example 31, perylene (Comparative Example 1), tetracene (Comparative Example 2), 2-cyanoperylene (the following formula, Comparative Example 3), 1-cyanotetracene (the following formula, Comparative Example) 4)
Was measured for the fluorescence quantum yield.

[0076]

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[0077]

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The results are shown below.Examples 37-42 3-cyanoperylene (Example 37), 3,
9-dicyanoperylene (Example 38), 3,4,9,1
0-tetracyanoperylene (Example 39), 5-cyano
Tetracene (Example 40), 5,12-dicyanotetra
Sene (Example 41), 5,6,11,12-tetracia
Using nottetracene (Example 42), the structure shown in FIG.
A stacked organic EL device was manufactured. Gala with ITO electrode 2
Substrate 1 with water, acetone or isopropyl alcohol.
Cleaning and vacuum evaporation equipment (1 × 10^-6torr, substrate temperature
TP as a hole transport layer 3 on the
D is 50 nm, and 3-cyanoperylate is formed thereon as the light emitting layer 4.
3,9-dicyanoperylene, 3,4,9,10-
Tracyanoperylene, 5-cyanotetracene, 5,12
-Dicyanotetracene or 5,6,11,12-tet
Lacyanotetracene of 10 nm, on which an electron transport layer 5
T-Bu-PBD to 50 nm, and furthermore, Al-
Li alloy 6 (Li: 0.5% by weight) was deposited to a thickness of 50 nm.
This element is charged with ITO as the positive electrode and Al-Li as the negative electrode.
Pressure, and at the emission start voltage and the applied voltage of 10V.
Emission luminance and emission color were observed. Comparative Examples 29 to 32 Perylene (Comparative Example 29), tetracene (ratio
Comparative Example 30), 2-cyanoperylene (Comparative Example 31), 1-
1 using cyanotetracene (Comparative Example 32).
A laminated organic EL device was manufactured. With ITO electrode 2
Glass substrate 1 is made of water, acetone, isopropyl alcohol
And a vacuum evaporation device (1 × 10 ^-6torr, group
(The plate temperature is room temperature).
TPD is 50 nm, and perylene and te are used as the light emitting layer 4 thereon.
Toracene, 2-cyanoperylene or 1-cyanotetra
Sen is 10 nm, and t-Bu-
PBD is 50 nm, and an Al-Li alloy 6 (L
i: 0.5% by weight). This element has I
Applying voltage with TO as the positive electrode and Al-Li as the negative electrode,
The light emission luminance and the light emission
And the emission color were observed. Examples 43-48 3-cyanoperylene (Example 43), 3,
9-dicyanoperylene (Example 44), 3,4,9,1
0-tetracyanoperylene (Example 45), 5-cyano
Tetracene (Example 46), 5,12-dicyanotetra
Sene (Example 47) or 5,6,11,12-tetra
Cyanotetracene (Example 48) and 9,9'-biant
A multilayer organic EL device having the structure shown in FIG.
Made. Glass substrate 1 with ITO electrode 2
Cleaning with isopropyl alcohol and vacuum deposition equipment
(1 × 10^-6torr, substrate temperature is room temperature)
On this, 50 nm of TPD is formed as a hole transport layer 3, and
3-cyanoperylene, 3,9-dicyano as the light emitting layer 4
Perylene, 3,4,9,10-tetracyanoperylene,
5-cyanotetracene, 5,12-dicyanotetracene
Or 5,6,11,12-tetracyanotetracene and
9,9'-bianthryl co-deposited layer (deposition ratio; each
Example 9,9'-bianthryl 9 minutes per molecule
) Is 10 nm, and t-Bu-
PBD is 50 nm, and an Al-Li alloy 6 (L
i: 0.5% by weight). This element has I
Applying voltage with TO as the positive electrode and Al-Li as the negative electrode,
The light emission luminance and the light emission
And the emission color were observed. Comparative Examples 33-36 Perylene (Comparative Example 33), tetracene (ratio
Comparative Example 34), 2-cyanoperylene (Comparative Example 35) or
1-cyanotetracene (Comparative Example 36) and 9,9'-via
1. A stacked organic EL device having a structure shown in FIG.
Was prepared. Glass substrate 1 with ITO electrode 2
Washed with isopropyl alcohol and vacuum deposited
Equipment (1 × 10^-6torr, substrate temperature is room temperature)
On top of this, 50 nm of TPD was
Perylene, tetracene, 2-cyano as light emitting layer 4
Perylene or 1-cyanotetracene and 9,9'-via
Layer with simultaneous deposition of toril (deposition ratio; each example molecule: 1 minute)
9,9'-bianthryl molecule) to 10 nm.
50 nm of t-Bu-PBD as an electron transport layer 5 on the
Further, an Al-Li alloy 6 (Li: 0.5 wt.
%) Was deposited to a thickness of 50 nm. A positive electrode of ITO, A
A voltage is applied with l-Li as the negative electrode,
And the emission luminance and emission color at 10V applied voltage
did.

The results are shown below. Emission start voltage (V) Emission luminance (cd / m ² , at 10 V) Emission color Example 7 3 1280 Blue green Example 8 3 1390 Green Example 9 3 1130 Yellow Example 10 3 1300 Green Example 11 3 1330 Yellow Example 12 3 1080 Orange Example 13 3 1520 Blue Green Example 14 3 1830 Green Example 15 3 1320 Yellow Example 16 3 1470 Green Example 17 3 1510 Yellow Example 18 3 1200 Orange Comparative Example 5 3 780 Blue Purple Comparison Example 6 6 70 Green Comparative Example 7 3 670 Blue Comparative Example 8 5 110 Yellow Comparative Example 9 3 910 Blue-violet Comparative Example 10 5 130 Green Comparative Example 11 3 950 Blue Comparative Example 12 5 190 Yellow

[0080]

According to the present invention, it is possible to provide a group of organic EL elements having high luminous efficiency and various luminescent colors. In addition, an organic EL display can be configured using this organic EL element.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of an organic EL device according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Anode electrode 3 ... Hole transport layer 4 ... Light emitting layer 5 ... Electron transport layer 6 ... Cathode electrode

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hiroyuki Sato 4-1-1, Kamiodanaka, Nakahara-ku, Kawasaki-shi, Kanagawa Prefecture Inside Fujitsu Limited (72) Inventor 4-1-1 Kamiodanaka, Nakahara-ku, Nakazaki-ku, Kawasaki-shi, Kanagawa Prefecture No. 1 Inside Fujitsu Limited

Claims (3)

[Claims] 1. A luminescent material represented by the following formulas 1, 2, 3,
4, 5, 6 and 7 (Wherein R ₁ represents H or —CN) (Wherein R ₂ and R ₃ represent an alkyl group, and R ₄ represents H or —NR ₂ R ₃ ) (Wherein R ₅ represents an alkyl group) (In the above formula, R ₆ represents H, F, Cl, —CN, an alkyl group or an aryl group.) (In the above formula, R ₇ represents an alkyl group, and R ₈ represents H, F, C
1, represents an alkyl group, an aryl group or —OR ₇ ) (Wherein R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each represent H or —CN, provided that R ₉ , R ₁₀ , R ₁₁ and R 12
_At least one of ₁₂ is -CN) (In the above formula, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ each represent H or —CN, provided that R ₁₃ , R ₁₄ , R ₁₅ and R _16
At least one of ₁₆ is -CN), an organic electroluminescence device comprising at least one selected from the group consisting of an anthracene derivative, a bianthryl derivative, a perylene derivative, and a tetracene derivative. 2. The organic electroluminescent device according to claim 1, further comprising 9,9'-bianthryl as a light emitting material. 3. An organic electroluminescence display comprising the organic electroluminescence device according to claim 1.