JP2002069063A - Phloxane compound and organic light emitting device using the same - Google Patents

Abstract

(57) [Summary] PROBLEM TO BE SOLVED: To provide a novel filter suitable as an organic layer of an organic light emitting device.
A loxane compound is provided. SOLUTION: It is represented by the following general formula [I].
A furoxane compound. Embedded image (Where R₁And R_TwoIs a substituted or unsubstituted ally
A substituted or unsubstituted heterocyclic group;₁You
And R_TwoMay be the same or different. R ₁And
And R_TwoMay form a ring. )

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel organic compound and an organic light emitting device using the same.

[0002]

2. Description of the Related Art In an organic light emitting device, a thin film containing a fluorescent organic compound is sandwiched between an anode and a cathode, and electrons and holes (holes) are injected from each electrode to exciton the fluorescent compound. It is an element that utilizes light emitted when this exciton is returned to the ground state.

In 1987, a study by Kodak Company (Appl.
Phys. Lett. 51, 913 (1987)), a function-separated type 2 using ITO as an anode, magnesium-silver alloy as a cathode, an aluminum quinolinol complex as an electron transporting material and a luminescent material, and a triphenylamine derivative as a hole transporting material. This device has a layered structure, and has an applied voltage of about 10 V and 1000 cd / m ^2.
A degree of luminescence has been reported. Related patents include U.S. Pat. No. 4,539,507 and U.S. Pat.
No. 32, U.S. Pat. No. 4,885,211 and the like.

[0004] In addition, by changing the type of the fluorescent organic compound, light emission from ultraviolet to infrared can be achieved, and various compounds have recently been actively studied. For example, US Pat. No. 5,151,629 and US Pat.
9,783, U.S. Pat. No. 5,382,477, JP-A-2-247278, JP-A-3-255190, JP-A-5-202356, JP-A-9-202
No. 878, Japanese Patent Application Laid-Open No. 9-227576, and the like.

[0005] In addition to the organic light-emitting device using the above low-molecular material, an organic light-emitting device using a conjugated polymer is also a group of Cambridge University (Nature,
347, 539 (1990)).
In this report, light emission was confirmed in a single layer by forming a film of polyphenylenevinylene (PPV) in a coating system.

US Pat. No. 5,247,190, US Pat. No. 5,514,878, and US Pat. No. 5,672,678 are related patents for organic light emitting devices using conjugated polymers.
JP-A-4-145192, JP-A-5-247
No. 460, for example.

As described above, recent advances in organic light-emitting elements are remarkable, and the characteristics thereof are that high luminance, a variety of emission wavelengths, high-speed response, a thin and lightweight light-emitting device can be realized at a low applied voltage. It suggests potential for a wide range of applications.

However, at present, light output with higher luminance or higher conversion efficiency is required. In addition, there are still many problems in terms of durability such as a change with time due to long-term use and deterioration due to an atmospheric gas containing oxygen or moisture. Further, when application to a full-color display or the like is considered, light emission of blue, green, and red with good color purity is required, but this problem is not yet sufficient.

As the fluorescent organic compound used for the electron transport layer, the light emitting layer, etc., many compounds having a heterocyclic ring have been studied. For example, a pyrrole compound, a thiophene compound, an oxazole compound, an oxadiazole compound and the like can be mentioned, but none of them have satisfactory light emission luminance and durability.

[0010]

An object of the present invention is to provide a novel furoxane compound.

It is another object of the present invention to provide an organic light-emitting device which uses the furoxane compound and has extremely high efficiency, high luminance and long life light output. Another object of the present invention is to provide an organic light-emitting device that has various emission wavelengths, exhibits various emission hues, and is extremely durable. Another object of the present invention is to provide an organic light emitting device that can be easily manufactured and can be manufactured at relatively low cost.

[0012]

Means for Solving the Problems The furoxan compound of the present invention is characterized by being represented by the following general formula [I].

[0013]

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(Wherein R ₁ and R ₂ represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and R ₁ and R ₂ may be the same or different. R ₁ and R ₂ may form a ring.)

The furoxane compound of the present invention is preferably a furoxan compound represented by the following general formulas [II] to [IV].

[0016]

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(Wherein, Ar₁And Ar_TwoIs a substitution or
Is an unsubstituted aryl group or a substituted or unsubstituted heterocyclic group
And Ar₁And Ar_TwoAre the same but different
May be. R_Three, R_Four, R_FiveAnd R₆Is an alkyl group,
Substituted or unsubstituted aralkyl group, substituted or unsubstituted
Represents a substituted aryl group or a substituted or unsubstituted heterocyclic group.
Then R _Three, R_Four, R_FiveAnd R₆Are the same but different
May be. )

[0018]

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(In the formula, Ar ₃ and Ar ₄ represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and Ar ₃ and Ar ₄ may be the same or different. R ₇ , R ₈ , R ₉ and R ₁₀ are a hydrogen atom,
Represents an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group or a cyano group, even if R ₇ , R ₈ , R ₉ and R ₁₀ are the same It may be different. )

[0020]

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(In the formula, Ar ₅ and Ar ₆ represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and Ar ₅ and Ar ₆ may be the same or different. R ₁₁ and R _12, an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, R ₁₁ and R ₁₂ may be different even in the same .R ₁₃ and R ₁₄ represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group or a cyano group, and even if R ₁₃ and R ₁₄ are the same, May be different.)

The organic light emitting device of the present invention is an organic light emitting device comprising at least a pair of electrodes comprising an anode and a cathode, and at least a layer containing one or more organic compounds sandwiched between the pair of electrodes. At least one layer containing a compound contains at least one of the furoxane compounds represented by the above general formula [I], preferably the above general formulas [II] to [IV].

In the organic light-emitting device of the present invention, it is preferable that at least the electron transport layer or the light-emitting layer among the layers containing the organic compound contains at least one of the above furoxane compounds.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The furoxan compound of the present invention is represented by the following general formula [I].

[0025]

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(In the formula, R ₁ and R ₂ represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and R ₁ and R ₂ may be the same or different. R ₁ and R ₂ may form a ring.)

The furoxane compound of the present invention is not particularly limited as long as it is represented by the above general formula [I], but is preferably one represented by the following general formulas [II] to [IV].

[0028]

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(Wherein, Ar₁And Ar_TwoIs a substitution or
Is an unsubstituted aryl group or a substituted or unsubstituted heterocyclic group
And Ar₁And Ar_TwoAre the same but different
May be. R_Three, R_Four, R_FiveAnd R₆Is an alkyl group,
Substituted or unsubstituted aralkyl group, substituted or unsubstituted
Represents a substituted aryl group or a substituted or unsubstituted heterocyclic group.
Then R _Three, R_Four, R_FiveAnd R₆Are the same but different
May be. )

[0030]

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(In the formula, Ar ₃ and Ar ₄ represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and Ar ₃ and Ar ₄ may be the same or different. R ₇ , R ₈ , R ₉ and R ₁₀ are a hydrogen atom,
Represents an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group or a cyano group, even if R ₇ , R ₈ , R ₉ and R ₁₀ are the same It may be different. )

[0032]

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(In the formula, Ar ₅ and Ar ₆ represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and Ar ₅ and Ar ₆ may be the same or different. R ₁₁ and R _12, an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, R ₁₁ and R ₁₂ may be different even in the same .R ₁₃ and R ₁₄ represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group or a cyano group, and even if R ₁₃ and R ₁₄ are the same, May be different.)

Specific examples of the substituents in the above general formulas [I] to [IV] are shown below.

As the aryl group, phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group,
Examples include a phenanthryl group, a fluorenyl group and a pyrenyl group.

Examples of the heterocyclic group include a thienyl group, a pyrrolyl group, a pyridyl group, a quinolyl group, a carbazolyl group, an oxazolyl group, an oxadiazolyl group, a terthienyl group and a terpyrrolyl group.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a ter-butyl group and an octyl group.

Examples of the aralkyl group include a benzyl group and a phenethyl group.

Examples of the substituent which the above substituent may have include alkyl groups such as methyl group, ethyl group and propyl group, aralkyl groups such as benzyl group and phenethyl group, phenyl group, naphthyl group, anthryl group and fluorenyl. Group, aryl group such as pyrenyl group, thienyl group, pyrrolyl group, pyridyl group, heterocyclic group such as quinolyl group, diethylamino group, dibenzylamino group, diphenylamino group, amino group such as ditolylamino group, methoxyl group,
Examples include an alkoxyl group such as an ethoxyl group, a propoxydyl group, and a phenoxyl group, a cyano group, and a nitro group.

Next, typical examples of the furoxane compound of the present invention are shown below, but the present invention is not limited thereto.

[0041]

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[0042]

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[0043]

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[0044]

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The furoxane compound of the present invention can be synthesized by a generally known method. For example, nitrile oxide is formed from an oxime, and various substituents are produced by a 1,3-dipolar cycloaddition reaction between nitrile oxides. Can be synthesized.

The furoxane compounds represented by the general formulas [I] to [IV] of the present invention are excellent in electron transporting property, light emitting property and durability as compared with conventional compounds. The layer containing the compound is particularly useful as an electron transporting layer and a light emitting layer, and a layer formed by a vacuum evaporation method, a solution coating method, or the like hardly causes crystallization or the like and has excellent stability over time.

Next, the organic light emitting device of the present invention will be described in detail.

The organic light emitting device of the present invention is an organic light emitting device comprising at least a pair of electrodes comprising an anode and a cathode, and at least a layer containing one or more organic compounds sandwiched between the pair of electrodes. At least one of the layers containing the general formula [I], preferably the general formula [I]
It is characterized by containing at least one of the furoxane compounds represented by I] to [IV].

In the organic light-emitting device of the present invention, it is preferable that at least the electron transport layer or the light-emitting layer among the layers containing an organic compound contains at least one of the above-mentioned furoxane compounds.

In the organic light emitting device of the present invention, the furoxane compounds represented by the above general formulas [I] to [IV] are formed between the anode and the cathode by a vacuum evaporation method or a solution coating method. The thickness of the organic layer is less than 10 μm, preferably 0.5 μm or less, more preferably 0.01 to 0.5 μm.
It is preferable to make the film as thin as possible.

FIGS. 1 to 3 show preferred examples of the organic light emitting device of the present invention.

FIG. 1 is a sectional view showing an example of the organic light emitting device of the present invention. FIG. 1 shows a structure in which an anode 2, a light emitting layer 3 and a cathode 4 are sequentially provided on a substrate. The light-emitting element used here is useful when it has a single hole-transporting ability, electron-transporting ability, and light-emitting performance, or when a mixture of compounds having the respective properties is used.

FIG. 2 is a sectional view showing another example of the organic light emitting device of the present invention. FIG. 2 shows a configuration in which an anode 2, a hole transport layer 5, an electron transport layer 6, and a cathode 4 are sequentially provided on a substrate 1. In this case, when the luminescent material has a hole transporting property or an electron transporting property or a material having both functions in each layer, and is used in combination with a mere hole transporting substance having no light emitting property or an electron transporting substance Useful for In this case, the light emitting layer 3 is made of either the hole transport layer 5 or the electron transport layer 6.

FIG. 3 is a sectional view showing another example of the organic light emitting device of the present invention. FIG. 3 shows a structure in which an anode 2, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6, and a cathode 4 are sequentially provided on a substrate 1. It separates the functions of carrier transport and light emission, and is used in a timely combination with a compound having hole transport, electron transport, and light emitting properties. Can be used, so that the emission hue can be diversified. Further, it is possible to effectively confine each carrier or exciton in the central light emitting layer 3 to improve the luminous efficiency.

However, FIGS. 1 to 3 show only very basic device configurations, and the configuration of the organic light-emitting device using the compound of the present invention is not limited to these. For example, various layer configurations such as providing an insulating layer at the interface between the electrode and the organic layer, providing an adhesive layer or an interference layer, and forming the hole transport layer from two layers having different ionization potentials can be employed.

The general formulas [I] to [I] used in the present invention
The furoxane compound represented by the formula [V] is a compound having excellent electron transporting properties, light emitting properties and durability as compared with conventional compounds, and can be used in any of the forms shown in FIGS.

In particular, the organic layer using the furoxane compound of the present invention is useful as an electron transporting layer and a light emitting layer.
Further, a layer formed by a vacuum evaporation method, a solution coating method, or the like hardly causes crystallization or the like and has excellent stability over time.

In the present invention, the furoxane compounds represented by the general formulas [I] to [IV] are used as constituents of the electron transport layer and the light emitting layer. Compounds or electron transporting compounds can be used together if necessary.

The following are examples of these compounds.

[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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In the organic light emitting device of the present invention, the layer containing the furoxane compounds represented by the general formulas [I] to [IV] and the layer containing another organic compound are generally formed by a vacuum evaporation method or a suitable solvent. And a thin film is formed by a coating method. In particular, when forming a film by a coating method, the film can be formed in combination with an appropriate binder resin.

The binder resin can be selected from a wide range of binder resins, for example, polyvinyl carbazole resin,
Polycarbonate resin, polyester resin, polyarylate resin, polystyrene resin, acrylic resin, methacrylic resin, butyral resin, polyvinyl acetal resin,
Examples include, but are not limited to, diallyl phthalate resin, phenol resin, epoxy resin, silicone resin, polysulfone resin, urea resin, and the like. These may be used alone or as a copolymer, alone or as a mixture of two or more.

The anode material preferably has a work function as large as possible. For example, simple metals such as gold, platinum, nickel, palladium, cobalt, selenium, and vanadium or alloys thereof, tin oxide, zinc oxide, indium tin oxide ( Metal oxides such as ITO) and indium zinc oxide can be used. In addition, conductive polymers such as polyaniline, polypyrrole, polythiophene, and polyphenylene sulfide can also be used. These electrode substances may be used alone or in combination of two or more.

On the other hand, the cathode material preferably has a small work function, such as lithium, sodium, potassium, calcium, magnesium, aluminum, indium, silver, and the like.
It can be used as a single metal or a plurality of alloys such as lead, tin and chromium. It is also possible to use metal oxidation such as indium tin oxide (ITO). Further, the cathode may have a single-layer structure or a multilayer structure.

The substrate used in the present invention is not particularly limited, but an opaque substrate such as a metal substrate or a ceramic substrate, or a transparent substrate such as glass, quartz, or a plastic sheet is used. Further, it is also possible to control the emitted light by using a color filter film, a fluorescent color conversion filter film, a dielectric reflection film or the like on the substrate.

It should be noted that a protective layer or a sealing layer may be provided on the fabricated device for the purpose of preventing contact with oxygen, moisture, or the like. Examples of the protective layer include a diamond thin film, an inorganic material film such as a metal oxide and a metal nitride, a polymer film such as a fluorine resin, a polyparaxylene, a polyethylene, a silicone resin, and a polystyrene resin, and a photocurable resin. Can be Alternatively, the device itself can be covered with glass, a gas impermeable film, metal, or the like, and the element itself can be packaged with an appropriate sealing resin.

[0077]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Compound no. Synthesis of 1 In a 300 ml three-necked flask, ditolylaminobenzaldehyde 10 g (33.2 mmol), ethanol 60 m
l and 60 ml of THF, 2.4 g (34.9 mmol) of hydroxylamine hydrochloride was added thereto with stirring at 5 ° C, and then 1.5 g of sodium hydroxide (36.5 mm).
ol) / water (30 ml) was added dropwise. After stirring at room temperature for 3 hours, water was added, the organic layer was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 10 g of oxime [1] (yellow crystals) (yield: 95%).

[0079]

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In a 200 ml three-necked flask, 3.0 g (9.5 mmol) of oxime [1] and 100 ml of dichloromethane were added, and 7.1 g (11.4 mmol) of antiformin (12% aqueous solution) was added dropwise with stirring at 0 ° C. Then 0.5 ml of triethylamine was added. After gradually raising the temperature and stirring at room temperature for 5 hours, the organic layer was extracted with chloroform, dried over anhydrous sodium sulfate, and purified with a silica gel column. 1 (yellow crystals)
4 g were obtained (yield 47%).

[0081]

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Example 2 Compound no. Synthesis of 6 Oxime [2] (white crystal) was synthesized in the same manner as in Example 1.

[0083]

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In a 200 ml three-necked flask, 3.0 g (20.1 mmol) of oxime [2], 50 ml of dichloromethane and 50 ml of THF were added and stirred at 0 ° C.
Antiformin (12% aqueous solution) 15.0 g (24.1 g)
mmol) was added dropwise. After the temperature was gradually raised and the mixture was stirred at room temperature for 5 hours, the organic layer was extracted with chloroform, dried over anhydrous sodium sulfate, and then purified on a silica gel column to obtain 1.2 g of a furoxane intermediate [3] (yellow crystals). Rate 41%).

[0085]

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In a 100 ml three-necked flask, 1.0 g (3.4 mmol) of the furoxane intermediate [3], 2.5 g (7.5 mmol) of the phosphonate compound and DMF
50 ml was added, and 0.99 (8.2 mmol) of potassium t-butoxide was added thereto while stirring at 5 ° C. After gradually raising the temperature and stirring at room temperature for 3 hours, water was added, the organic layer was extracted with ethyl acetate, dried over anhydrous sodium sulfate, purified on a silica gel column, and purified with a furoxane compound No. 1 6 (yellow crystals)
6 g was obtained (yield 73%).

[0087]

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Example 3 Compound no. Synthesis of 11 4.7 g of oxime [1] in a 200 ml three-necked flask
(15.0 mmol), 2.2 g of oxime [2] (1
5.0 mmol), 50 ml of dichloromethane and TH
F50ml, and stirred at 0 ° C with antiformin (1
22.3 g (36.0 mmol) of a 2% aqueous solution was added dropwise. After gradually heating and stirring at room temperature for 5 hours, the organic layer was extracted with chloroform, dried over anhydrous sodium sulfate, and then purified on a silica gel column to obtain 2.6 g of a furoxane intermediate [4] (yellow crystals) (yield). Rate 38%).

[0089]

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Dry THF 5 was placed in a 100 ml three-necked flask.
After adding 0 ml, and stirring at 5 ° C., 0.13 g (2.4 mmol) of sodium methoxide was added, and then 0.15 g (2.3 mmol) of dicyanomethylene was added.
After stirring for 30 minutes, at room temperature, 1.0 g of a furoxane intermediate [4]
(2.2 mmol) / 10 ml of THF was added dropwise,
After stirring for 2 hours and further stirring at 60 ° C. for 1 hour, water was added, and the organic layer was extracted with ethyl acetate, dried over anhydrous sodium sulfate, purified on a silica gel column, and purified with a furoxane compound No. 1 0.8 g of 11 (red crystals) was obtained (yield: 72).
%).

[0091]

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Example 4 Compound no. Synthesis of 14 Oxime [5] (white crystal) was synthesized in the same manner as in Example 1.

[0093]

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A 200 ml three-necked flask was charged with 3.0 g (12.2 mmol) of oxime [5], 50 ml of dichloromethane and 50 ml of THF, and stirred at 0 ° C.
9.1 g (14.7 m) of antiformin (12% aqueous solution)
mol) was added dropwise. After gradually raising the temperature and stirring at room temperature for 5 hours, the organic layer was extracted with chloroform, dried over anhydrous sodium sulfate, and purified with a silica gel column. 1.5 g of 14 (yellow crystals) was obtained (yield 51).
%).

[0095]

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Example 5 An element having the structure shown in FIG. 2 was prepared.

A glass substrate as a substrate 1 was coated with indium tin oxide (ITO) as an anode 2 by sputtering.
A film having a thickness of 20 nm was used as a transparent conductive support substrate. This was ultrasonically washed with acetone and isopropyl alcohol (IPA) sequentially, then washed with boiling IPA and dried. Further, the substrate subjected to UV / ozone cleaning was used as a transparent conductive support substrate.

A compound represented by the following structural formula was formed into a film having a thickness of 60 nm on a transparent conductive support substrate by a vacuum evaporation method to form a hole transport layer 5.

[0099]

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Further, Compound No. Flow indicated by 6
Xanthane compound is deposited to a thickness of 60 nm by vacuum evaporation.
Thus, an electron transport layer 6 was formed. The degree of vacuum at the time of vapor deposition is 1.0 ×
10 ^-FourPa, the film formation rate is 0.2 to 0.3 nm / sec.
The film was formed under the conditions.

Next, using a vapor deposition material composed of aluminum and lithium (lithium concentration 1 atomic%) as the cathode 4, a 150 nm thick film was formed on the organic layer by a vacuum vapor deposition method.
m of the metal layer film was formed. The degree of vacuum during vapor deposition is 1.0 × 1
The film was formed under the conditions of 0 ^-4 Pa and a film formation speed of 1.0 to 1.2 nm / sec.

When a DC voltage of 8 V was applied to the device thus obtained with an ITO electrode (anode 2) as a positive electrode and an Al-Li electrode (cathode 4) as a negative electrode, 8.2 mA / cm ²
A current was passed through the device at a current density of, and blue light emission was observed at a luminance of 470 cd / m ² .

Further, the current density was increased to 7.0 under a nitrogen atmosphere.
When a voltage was applied for 100 hours while maintaining the current at mA / cm ² ,
380 cd after 100 hours from initial luminance 420 cd / m ²
/ M ² and the luminance degradation was small.

Examples 6 to 11 Exemplified Compound Nos. In place of Exemplified Compound No. 6, 2,8,9,12,15,1
A device was prepared in the same manner as in Example 5, except that the electron transporting layer 6 was formed using No. 7, and the same evaluation was performed. Table 1 shows the results.

[Comparative Example 1] 6 and a compound represented by the following structural formula is used.
A device was prepared in the same manner as in Example 5 except that the device was formed, and the same evaluation was performed. Table 1 shows the results.

[0106]

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[0107]

[Table 1]

Example 12 An element having the structure shown in FIG. 2 was prepared.

As in Example 5, a hole transport layer 5 was formed on a transparent conductive support substrate. Further, the exemplified compound No.
The electron transport layer 6 was formed by forming a film of a furoxane compound represented by No. 11 and aluminum trisquinolinol (weight ratio 1:20) to a thickness of 60 nm by a vacuum evaporation method. The degree of vacuum during vapor deposition is 1.0 × 10 ⁻⁴ Pa, and the film formation rate is 0.2
~ 0.3. The film was formed under the condition of nm / sec.

Next, using a vapor deposition material composed of aluminum and lithium (lithium concentration 1 atomic%) as the cathode 4, a 150 nm thick film was formed on the organic layer by a vacuum vapor deposition method.
m of the metal layer film was formed. The degree of vacuum during vapor deposition is 1.0 × 1
The film was formed under the conditions of 0 ^-4 Pa and a film formation speed of 1.0 to 1.2 nm / sec.

When a DC voltage of 8 V was applied to the device thus obtained with the ITO electrode (anode 2) serving as a positive electrode and the Al-Li electrode (cathode 4) serving as a negative electrode, 8.7 mA / cm ²
A current flowed through the device at a current density of, and orange light emission was observed at a luminance of 760 cd / m ² .

Further, the current density was increased to 7.0 under a nitrogen atmosphere.
When a voltage was applied for 100 hours while maintaining the current at mA / cm ² ,
580 cd after 100 hours from the initial luminance of 680 cd / m ²
/ M ² and the luminance degradation was small.

[Examples 13 to 18] Compounds Nos. 1
In place of Exemplified Compound No. 1, 1,4,5,13,1
Example 1 except that the electron transport layer 6 was formed using 4, 16
An element was prepared in the same manner as in Example 2, and the same evaluation was performed. Table 2 shows the results.

[Comparative Example 2] In place of Comparative Compound No. 11, Comparative Compound No. A device was prepared in the same manner as in Example 12 except that the electron transport layer 6 was formed using No. 1, and the same evaluation was performed. Table 2 shows the results.

[0115]

[Table 2]

[Embodiment 19] An element having the structure shown in FIG. 3 was produced.

In the same manner as in Example 5, a hole transport layer 5 was formed on a transparent conductive support substrate. Next, the exemplified compound No. 1
The furoxane compound represented by the formula 0
The light emitting layer 3 was formed in a thickness of nm. Further, an electron transport layer 6 was formed by depositing aluminum trisquinolinol to a thickness of 40 nm by a vacuum deposition method. The degree of vacuum during the deposition is 1.0 × 10 ⁻⁴ Pa, and the film formation rate is 0.2 to 0.3 nm.
/ Sec.

Next, using a vapor deposition material composed of aluminum and lithium (lithium concentration 1 atomic%) as the cathode 4, a 150 nm thick film was formed on the organic layer by a vacuum vapor deposition method.
m of the metal layer film was formed. The degree of vacuum during vapor deposition is 1.0 × 1
The film was formed under the conditions of 0 ^-4 Pa and a film formation speed of 1.0 to 1.2 nm / sec.

When a DC voltage of 10 V was applied to the thus obtained device with the ITO electrode (anode 2) serving as a positive electrode and the Al—Li electrode (cathode 4) serving as a negative electrode, 12.0 mA / c was obtained.
current flows through the device at a current density of m ^2, 1170cd / m ²
Light emission was observed at a luminance of.

Further, the current density was increased to 10. under a nitrogen atmosphere.
When a voltage was applied for 100 hours while maintaining the current at 0 mA / cm ² , 900 hours after the initial luminance of 980 cd / m ^2, 900
The luminance degradation was small at cd / m ² .

[Examples 20 to 21] Compounds Nos. 1
0 in place of Exemplified Compound No. Light emitting layer 3 using 3, 7
A device was prepared in the same manner as in Example 19 except that was formed, and the same evaluation was performed. Table 3 shows the results.

Comparative Example 3 Exemplified Compound No. In place of Comparative Compound No. 10, A device was prepared in the same manner as in Example 19 except that the light-emitting layer 3 was formed using No. 1, and the same evaluation was performed. Table 3 shows the results.

[0123]

[Table 3]

Example 22 An element having the structure shown in FIG. 1 was produced.

On the transparent conductive support substrate used in Example 5, Exemplified Compound No. A solution obtained by dissolving 0.050 g of the furoxane compound represented by No. 6 and 1.00 g of poly-N-vinylcarbazole (weight average molecular weight = 63,000) in 80 ml of chloroform was subjected to a spin coating method (rotational speed =
The organic layer (light emitting layer 3) was formed at a film thickness of 120 nm at 2000 rpm).

Next, using a vapor deposition material composed of aluminum and lithium (lithium concentration: 1 atomic%) as the cathode 4, a 150 nm thick film was formed on the organic layer by vacuum vapor deposition.
m of the metal layer film was formed. The degree of vacuum during vapor deposition is 1.0 × 1
The film was formed under the conditions of 0 ^-4 Pa and a film formation speed of 1.0 to 1.2 nm / sec.

When a DC voltage of 10 V was applied to the thus obtained device with the ITO electrode (anode 2) serving as a positive electrode and the Al-Li electrode (cathode 4) serving as a negative electrode, 7.6 mA / cm
Current flows through the element at a ^second current density, a blue light emission was observed at a luminance of 450 cd / m ^2.

[Comparative Example 4] In place of Comparative Compound No. 6, A device was prepared in the same manner as in Example 22 except that the light-emitting layer 3 was formed by using Example No. 1. When a DC voltage of 10 V was applied in the same manner, a current flowed through the device at a current density of 8.1 mA / cm ² and 40 cd Blue light emission was observed at a luminance of / m ² .

[0129]

As described above, the novel furoxane compounds represented by the general formulas [I] to [IV] of the present invention can be suitably used as an organic layer of an organic light emitting device.

The organic light-emitting device using these furoxane compounds can emit light with high luminance at a low applied voltage and has excellent durability. In particular, the organic layer containing the furoxane compound of the present invention is excellent as an electron transporting layer and also excellent as a light emitting layer.

Further, the device can be prepared by using a vacuum deposition method or a casting method, and a relatively inexpensive and large-area device can be easily prepared.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of an organic light emitting device according to the present invention.

FIG. 2 is a cross-sectional view illustrating another example of the organic light emitting device according to the present invention.

FIG. 3 is a cross-sectional view illustrating another example of the organic light emitting device according to the present invention.

[Explanation of symbols]

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

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Andreessen Sven 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (reference) 3K007 AB00 AB02 AB03 AB04 AB18 BB06 CA01 CA02 CA04 CA06 CB01 DA00 DB03 EB00 FA01 FA02 FA03 4C056 AA01 AB02 AC04 AD01 AE03 AF01 FA04 FA14 FA16 FB01 FC07

Claims (9)

[Claims] 1. A compound represented by the following general formula [I]:
A furoxane compound. Embedded image(Where R₁And R_TwoIs a substituted or unsubstituted ally
A substituted or unsubstituted heterocyclic group;₁You
And R_TwoMay be the same or different. R ₁And
And R_TwoMay form a ring. ) 2. A compound represented by the following general formula [II]:
2. The furoxan compound according to claim 1, which is a feature. Embedded image(Wherein, Ar₁And Ar_TwoIs a substituted or unsubstituted
A reel group, a substituted or unsubstituted heterocyclic group,
r₁And Ar_TwoThey may be the same or different. R
_Three, R_Four, R_FiveAnd R₆Is an alkyl group, substituted or unsubstituted
Substituted aralkyl group, substituted or unsubstituted aryl
A substituted or unsubstituted heterocyclic group; _Three,
R_Four, R_FiveAnd R₆May be the same or different
No. ) 3. The furoxan compound according to claim 1, which is represented by the following general formula [III]. Embedded image (Wherein, Ar ₃ and Ar ₄ represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group;
r ₃ and Ar ₄ may be the same or different.
R ₇ , R ₈ , R ₉ and R ₁₀ represent a hydrogen atom, an alkyl group,
Represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group or a cyano group, wherein R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different. Is also good. ) 4. The furoxan compound according to claim 1, which is represented by the following general formula [IV]. Embedded image (Wherein, Ar ₅ and Ar ₆ represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group;
r ₅ and Ar ₆ may be the same or different.
R ₁₁ and R ₁₂ represent an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group,
R ₁₁ and R ₁₂ may be the same or different.
R ₁₃ and R ₁₄ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group or a cyano group, and R ₁₃ and R ₁₄ are the same. Or different. ) 5. A pair of electrodes comprising an anode and a cathode,
One or more organic compounds sandwiched between a pair of electrodes
An organic light-emitting device having at least a layer containing
At least one of the layers containing an organic compound has the following general formula
At least one of the furoxane compounds represented by [I]
An organic light-emitting device comprising: Embedded image(Where R₁And R_TwoIs a substituted or unsubstituted ally
A substituted or unsubstituted heterocyclic group;₁You
And R_TwoMay be the same or different. R ₁And
And R_TwoMay form a ring. ) 6. The furoxan compound represented by the following general formula:
It is a furoxan compound represented by [II].
The organic light emitting device according to claim 5, wherein Embedded image(Wherein, Ar₁And Ar_TwoIs a substituted or unsubstituted
A reel group, a substituted or unsubstituted heterocyclic group,
r₁And Ar_TwoMay be the same or different.
R_Three, R_Four, R_FiveAnd R₆Is an alkyl group, substituted or
Unsubstituted aralkyl group, substituted or unsubstituted aryl
A substituted or unsubstituted heterocyclic group; _Three,
R_Four, R_FiveAnd R₆May be the same or different
No. ) 7. The organic light emitting device according to claim 5, wherein the furoxan compound is a furoxan compound represented by the following general formula [III]. Embedded image (Wherein, Ar ₃ and Ar ₄ represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group;
r ₃ and Ar ₄ may be the same or different.
R ₇ , R ₈ , R ₉ and R ₁₀ represent a hydrogen atom, an alkyl group,
Represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group or a cyano group, wherein R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different. Is also good. ) 8. The organic light emitting device according to claim 5, wherein the furoxane compound is a furoxan compound represented by the following general formula [IV]. Embedded image (Wherein, Ar ₅ and Ar ₆ represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group;
r ₅ and Ar ₆ may be the same or different.
R ₁₁ and R ₁₂ represent an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group,
R ₁₁ and R ₁₂ may be the same or different.
R ₁₃ and R ₁₄ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group or a cyano group, and R ₁₃ and R ₁₄ are the same. Or different. ) 9. The organic light emitting device according to claim 5, wherein at least one of the electron transport layer and the light emitting layer among the layers containing the organic compound contains at least one of the furoxane compounds.