WO2015125581A1 - 有機電界発光素子 - Google Patents
有機電界発光素子 Download PDFInfo
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- WO2015125581A1 WO2015125581A1 PCT/JP2015/052504 JP2015052504W WO2015125581A1 WO 2015125581 A1 WO2015125581 A1 WO 2015125581A1 JP 2015052504 W JP2015052504 W JP 2015052504W WO 2015125581 A1 WO2015125581 A1 WO 2015125581A1
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- light emitting
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- organic
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical class [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/805—Electrodes
- H10K59/8052—Cathodes
- H10K59/80524—Transparent cathodes, e.g. comprising thin metal layers
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/82—Cathodes
- H10K50/828—Transparent cathodes, e.g. comprising thin metal layers
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
- H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
- H10K50/131—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit with spacer layers between the electroluminescent layers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K50/81—Anodes
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
- H10K50/818—Reflective anodes, e.g. ITO combined with thick metallic layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/82—Cathodes
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/854—Arrangements for extracting light from the devices comprising scattering means
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/32—Stacked devices having two or more layers, each emitting at different wavelengths
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- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/805—Electrodes
- H10K59/8051—Anodes
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/805—Electrodes
- H10K59/8051—Anodes
- H10K59/80518—Reflective anodes, e.g. ITO combined with thick metallic layers
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/805—Electrodes
- H10K59/8052—Cathodes
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/875—Arrangements for extracting light from the devices
- H10K59/877—Arrangements for extracting light from the devices comprising scattering means
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- H—ELECTRICITY
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- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/351—Thickness
Definitions
- the present invention relates to an organic electroluminescent element.
- An organic electroluminescence device (so-called organic EL device) using electroluminescence (hereinafter referred to as EL) of an organic material is a thin-film type completely solid device capable of emitting light at a low voltage of several V to several tens V. It has many excellent features such as high brightness, high luminous efficiency, thinness, and light weight. For this reason, it has been attracting attention in recent years as surface light emitters such as backlights for various displays, display boards such as signboards and emergency lights, and illumination light sources.
- Such an organic EL element has a structure in which a light emitting layer composed of an organic material is sandwiched between two electrodes, and emitted light generated in the light emitting layer passes through the electrode and is extracted outside. For this reason, at least one of the two electrodes is configured as a transparent electrode.
- an oxide semiconductor material such as indium tin oxide (SnO 2 —In 2 O 3 : Indium Tin Oxide: ITO) is generally used. Studies aiming at resistance have also been made (see, for example, Patent Document 1). However, since ITO uses rare metal indium, the material cost is high, and it is necessary to anneal at about 300 ° C. after film formation in order to reduce resistance.
- a specific wavelength is strengthened in an organic EL element in which multiple reflection occurs between a transparent electrode and a reflective electrode. That is, a specific wavelength can be strengthened in the light that can be extracted from the organic EL element by multiple reflection. For this reason, multiple reflection is generated between the transparent electrode and the reflective electrode to increase the specific wavelength, thereby causing a bias in the wavelength of light that can be extracted from the organic EL element.
- an organic EL element when used for a wide viewing angle liquid crystal backlight or the like, it is required to reduce the viewing angle dependency.
- a metal layer is used for a transparent electrode and a specific wavelength is strengthened by multiple reflection, the wavelength of the light that can be extracted is biased, resulting in emission light with high wavelength dependency with reduced uniformity and a viewing angle. Dependency occurs.
- an organic EL element using a metal layer for such a transparent electrode it is required to suppress viewing angle dependency.
- the present invention provides an organic electroluminescent device having little viewing angle dependency.
- the organic electroluminescent element of the present invention comprises a transparent electrode mainly composed of silver (Ag), a reflective electrode made of metal, and at least one light emitting layer provided between the transparent electrode and the reflective electrode. Prepare. The difference between the maximum value and the minimum value of the element reflectivity in the light with a wavelength of 450 nm to 750 nm of the organic electroluminescent element is within 30%.
- the difference between the maximum value and the minimum value of the element reflectivity in light having a wavelength of 450 nm to 750 nm is set within 30%, whereby the reflectivity of each wavelength in the organic electroluminescent element is reduced. It can be made uniform. For this reason, the light extracted from the organic electroluminescent element is light with high uniformity of each wavelength without being biased by the specific wavelength being strengthened. Therefore, the wavelength dependence due to multiple reflection can be suppressed, and an organic electroluminescence device with little viewing angle dependence can be provided.
- 6 is a graph simulating the relationship between the reflectance of a transparent electrode and the difference between the maximum value and the minimum value of element reflectivity (element reflectivity difference) in light having a wavelength of 450 nm to 750 nm. It is a figure for demonstrating the element structure for calculating
- 5 is a graph simulating the relationship between the reflectance of a reflective electrode and the difference between the maximum value and the minimum value of element reflectivity (element reflectivity difference) in light having a wavelength of 450 nm to 750 nm.
- FIG. 6 is a graph simulating the relationship between the thickness of a light emitting unit and the difference between the maximum value and the minimum value of element reflectivity (element reflectivity difference) in light having a wavelength of 450 nm to 750 nm. It is a figure which shows the structural formula of TBAC and Ir (ppy) 3 for demonstrating the coupling
- FIG. 2 is a diagram showing a structural formula and molecular orbital of a ⁇ -carboline ring. It is a cross-sectional schematic diagram of the organic electroluminescent element (organic EL element) of 2nd Embodiment. It is a cross-sectional schematic diagram of the organic electroluminescent element (organic EL element) of the modification of 2nd Embodiment.
- FIG. 1 the cross-sectional schematic diagram of the organic electroluminescent element (organic EL element) of this embodiment is shown.
- the organic EL element 10 is provided to face a substrate 11, a nitrogen-containing layer 12 provided on the substrate 11, a transparent electrode 13 formed in contact with the nitrogen-containing layer 12, and the transparent electrode 13.
- a light emitting unit 14 sandwiched between the transparent electrode 13 and the reflective electrode 15.
- the light emitting unit 14 has at least one light emitting layer. Details of each configuration of the substrate 11, the nitrogen-containing layer 12, the transparent electrode 13, the light emitting unit 14, and the reflective electrode 15 will be described later.
- the organic EL element 10 is designed such that the difference between the maximum value and the minimum value of the element reflectivity for light having a wavelength of 450 nm to 750 nm is within 30%.
- the element reflectivity is the reflectivity of the organic EL element 10 with respect to light incident from the front (0 to 10 °) on the substrate 11 side when the organic EL element 10 is not emitting light. It can be obtained with a vessel.
- required by the structure except a light-scattering structure be an element reflectance of an organic EL element.
- FIG. 2 shows a graph simulating the relationship between the reflectance of the transparent electrode 13 and the difference between the maximum value and the minimum value of the element reflectivity (element reflectivity difference) in light having a wavelength of 450 nm to 750 nm.
- the horizontal axis indicates the reflectance of the transparent electrode 13.
- the reflectance of the transparent electrode 13 is such that after forming a nitrogen-containing layer 12 on a glass substrate 11 with a thickness of 75 nm, the transparent electrode 13 made of silver (Ag) is in contact with the nitrogen-containing layer 12. It calculated
- the transparent electrode 13 changes the thickness of (Ag) between 6 and 15 nm in increments of 1 nm, and calculates the average reflectance of light with a wavelength of 450 nm to 750 nm irradiated from the substrate 11 side at each thickness.
- the reflectance was 13.
- the vertical axis represents the difference between the maximum value and the minimum value of the element reflectivity for light having a wavelength of 450 nm to 750 nm.
- the maximum value and the minimum value of the element reflectivity were obtained by the organic EL element 10 having the configuration shown in FIG.
- the nitrogen-containing layer 12 was 75 nm
- the organic material was 220 nm as the light emitting unit 14, and aluminum was 100 nm as the reflective electrode 15.
- the element reflectivity of each wavelength was obtained in steps of 1 nm between wavelengths of 450 nm to 750 nm.
- the reflectivity of the transparent electrode 13 needs to be 35% or less.
- the average reflectance of light with a wavelength of 450 nm to 750 nm of the transparent electrode 13 was about 33% at a thickness of 10 nm and about 36% at a thickness of 11 nm.
- the thickness of the transparent electrode 13 needs to be less than 11 nm, preferably 10 nm or less.
- the transparent electrode 13 In order to reduce the reflectance of the transparent electrode 13, it is necessary to form the transparent electrode 13 to be thin and to have a configuration that does not deteriorate the light transmission characteristics even if the transparent electrode 13 is thinly formed.
- the light transmission characteristics are affected by the material and thickness of the transparent electrode 13 and the surface shape of the transparent electrode 13. That is, in order to reduce the reflectance of the transparent electrode 13, it is necessary to form a metal layer having high uniformity and flatness even if it is formed thin.
- the transparent electrode 13 is formed of a metal
- the transparent electrode 13 is formed thin in order to improve the light transmittance, aggregation of metal atoms tends to occur, and the uniformity of the metal layer tends to decrease. For this reason, viewing angle dependence occurs due to interference with a specific wavelength.
- the specific wavelength is increased or decreased due to interference with the period of the unevenness. If it does so, the specific wavelength dependence will generate
- the surface shape of the transparent electrode 13 has high surface uniformity and flatness. Due to the high flatness, interference with a specific wavelength can be suppressed. Further, by increasing the uniformity of the surface, interference at this specific wavelength can be suppressed, and wavelength dependency can be suppressed.
- the transparent electrode 13 is formed of silver or an alloy containing silver as a main component. Further, as a base for forming the transparent electrode 13, the number of unshared electron pairs that are not involved in aromaticity and not coordinated to the metal among the unshared electron pairs of the nitrogen atom (N) is represented by n, molecular weight It is preferable to form the nitrogen-containing layer 12 having a compound in which the effective unshared electron pair content [n / M] is 2.0 ⁇ 10 ⁇ 3 ⁇ [n / M] where is M.
- the transparent electrode 13 with high uniformity can be formed even when the metal layer is formed to a thickness of about 4 nm. . Details of the silver-containing layer constituting the transparent electrode 13 and the nitrogen-containing layer 12 serving as a base will be described later.
- FIG. 4 shows a graph simulating the relationship between the reflectivity of the reflective electrode 15 and the difference between the maximum value and the minimum value of element reflectivity (element reflectivity difference) in light having a wavelength of 450 nm to 750 nm.
- the horizontal axis indicates the reflectance of the reflective electrode 15.
- the reflectance of the reflective electrode 15 was determined for an element in which the reflective electrode 15 was formed to 100 nm on a glass substrate 11 as shown in FIG.
- the reflective electrode 15 was formed by changing the material to be formed, and the average reflectance of light having a wavelength of 450 nm to 750 nm irradiated on the reflective electrode 15 in each material was used as the reflectance of the reflective electrode 15.
- the vertical axis indicates the difference between the maximum value and the minimum value of the element reflectivity for light having a wavelength of 450 nm to 750 nm.
- the maximum value and the minimum value of the element reflectivity were obtained by the organic EL element 10 having the configuration shown in FIG.
- the nitrogen-containing layer 12 was 75 nm
- the transparent electrode 13 was silver 10 nm
- the light emitting unit 14 was organic material 220 nm.
- the element reflectivity of each wavelength was obtained in increments of 1 nm between wavelengths of 450 nm to 750 nm.
- the reflectance of the reflective electrode 15 increases, the difference between the maximum value and the minimum value of the element reflectance decreases.
- the reflectivity of the reflective electrode 15 needs to be 90% or more.
- the reflectance of the reflective electrode 15 by increasing the reflectance of the reflective electrode 15, highly uniform reflection can be performed for all wavelengths. Further, by increasing the reflectance, it is possible to suppress the absorption of the specific wavelength, and it is possible to suppress the attenuation of the specific wavelength of the reflected light. That is, the effect that the specific wavelength of reflected light is strengthened or weakened by the microcavity effect can be suppressed. Therefore, by increasing the reflectance of the reflective electrode 15, the influence of the reflective electrode 15 on the specific wavelength in the organic EL element 10 can be suppressed, and highly uniform light can be obtained. For this reason, the wavelength dependence of the light taken out from the organic EL element 10 and the viewing angle dependence can be suppressed.
- Reflectance of reflective electrode In order to increase the reflectance of the reflective electrode 15, a material having a high reflectance is used. For example, it is preferable to use silver, aluminum, or the like that exhibits a reflectance of 90% or more in the above simulation.
- the reflective electrode 15 is used as the cathode of the organic EL element 10, it is preferable to use aluminum having a high electron injection property.
- silver in order to enhance the electron injecting property, for example, it is possible to form aluminum with a thickness of about 1 nm between silver and the light emitting unit 14, and the cathode can have a laminated structure of silver and aluminum. is there.
- the thickness of the aluminum is very thin, about 1 nm. It becomes possible to raise.
- the configuration of the light emitting unit 14 by improving the electron injecting property by the configuration of the light emitting unit 14, it is possible to adopt a configuration in which silver is in direct contact with the light emitting unit 14. For example, by using a mixture of an organic material and an inorganic salt / complex for the layer in contact with silver, the electron injection property to the light emitting unit 14 can be improved. For this reason, the reflective electrode 15 made of silver can be formed without reducing the reflectance.
- the surface shape of the reflective electrode 15 is preferably high in surface uniformity and flatness. Due to the high flatness, the wavelength interference is small. For example, when irregularities with a specific period are present on the surface, when light is reflected by the reflective electrode 15, the specific wavelength is strengthened or weakened due to interference with the period of the irregularities. For this reason, specific wavelength dependence will occur. By increasing the flatness of the surface, interference with the specific wavelength can be suppressed, and therefore wavelength dependency can be suppressed.
- the reflective electrode 15 when the reflective electrode 15 is formed of silver or an alloy containing silver as a main component, as in the case of the transparent electrode 13 described above, the non-shared electron pair of the nitrogen atom (N) as an underlayer is made aromatic.
- the effective unshared electron pair content [n / M] is 2.0 ⁇ 10 ⁇ 3 ⁇ [n, where n is the number of unshared electron pairs that are not involved and are not coordinated to the metal, and the molecular weight is M. / M] is preferable to form the nitrogen-containing layer 12 having a compound.
- the reflective electrode 15 is used as a cathode, it is particularly preferable to use a material having a high electron transporting property among the nitrogen-containing compounds.
- FIG. 6 shows a graph simulating the relationship between the thickness of the light emitting unit 14 and the difference between the maximum value and the minimum value of element reflectivity (element difference in element reflectivity) for light having a wavelength of 450 nm to 750 nm.
- the horizontal axis indicates the thickness of the light emitting unit 14.
- the thickness of the light emitting unit 14 is changed to an organic material by changing the thickness of the light emitting unit 14 formed between the transparent electrode 13 and the reflective electrode 15 in increments of 10 nm between 80 nm and 400 nm. A layer was formed.
- the vertical axis indicates the difference between the maximum value and the minimum value of the element reflectivity for light having a wavelength of 450 nm to 750 nm.
- the maximum value and the minimum value of the element reflectivity were obtained by the organic EL element 10 having the configuration shown in FIG.
- the nitrogen-containing layer 12 was 75 nm
- the transparent electrode 13 was silver 10 nm
- the reflective electrode 15 was aluminum 100 nm.
- the element reflectivity of each wavelength was obtained in increments of 1 nm between wavelengths 450 nm and 750 nm.
- the difference between the maximum value and the minimum value of the element reflectivity in light having a wavelength of 450 nm to 750 nm changes. This is because even if the light emitting unit 14 has the same thickness, the element reflectivity changes in a complicated manner for each wavelength, and the element reflectivity of each wavelength changes according to the thickness of the light emitting unit 14. by. That is, in the organic EL element 10, the thickness of the light emitting unit 14 provided between the transparent electrode 13 and the reflective electrode 15 affects the element reflectance of each wavelength.
- the light emitting unit 14 when the light emitting unit 14 is set to a thickness that easily interferes with a specific wavelength in the light that is multiple-reflected between the transparent electrode 13 and the reflective electrode 15, the amplification or attenuation of the specific wavelength that is subject to interference may occur. Occurs and the specific wavelength of the reflected light is intensified or weakened.
- the element reflectivity at each wavelength is lower than the thickness of the light emitting unit 14, for example, at a certain thickness, the reflectivity decreases on the short wavelength side, and at a different thickness, the reflectivity decreases in the intermediate wavelength range.
- the difference between the maximum value and the minimum value of the element reflectivity is 30%. It is necessary to design the light emitting unit 14 with a thickness within the range. That is, it is preferable that the thickness of the light emitting unit 14 of the organic EL element 10 is designed to be a thickness that does not easily interfere with a specific wavelength.
- the light emitting unit 14 performs a simulation as described above, and obtains a difference between the maximum value and the minimum value of the element reflectivity in light having a wavelength of 450 nm to 750 nm, so that the difference is within 30%.
- the thickness is such that the difference between the maximum value and the minimum value of the element reflectivity in light with a wavelength of 450 nm to 750 nm is within 30%, 130 nm or less, 190 nm, 220 nm, or 270 to 310 nm. Any one of these may be set as the thickness of the light emitting unit 14 to constitute the organic EL element 10.
- the thickness of the light emitting unit 14 in the organic EL element 10 is a layer formed between the transparent electrode 13 and the reflective electrode 15, and has at least one light emitting layer.
- the light emitting unit 14 may be a single layer or a plurality of layers may be stacked.
- a so-called tandem structure in which a plurality of light emitting layers are stacked may be used. Even in these cases, the total thickness of all the layers formed between the transparent electrode 13 and the reflective electrode 15 is the thickness of the light emitting unit 14 in the organic EL element 10.
- the graph showing the difference (element reflectance difference) between the maximum value and the minimum value of the element reflectivity in light with a wavelength of 450 nm to 750 nm is a complicated behavior as described above. Tend to show.
- the graph showing the element reflectivity difference in light having a wavelength of 450 nm to 750 nm has a periodically stable behavior.
- the thickness of the light emitting unit 14 is 220 nm. From the graph shown in FIG. 6, when the thickness of the light emitting unit 14 is 220 nm, the element reflectance difference for light with a wavelength of 450 nm to 750 nm is within 30%, but it is about 29%, which is slightly less than 30%. For this reason, when the thickness of the light emitting unit 14 is 220 nm, the reflectance of the transparent electrode 13 or the reflection of the reflective electrode 15 is required in order to make the element reflectance difference within the wavelength of 450 nm to 750 nm within 30%.
- the difference in element reflectivity for light with a wavelength of 450 nm to 750 nm is significantly lower than 30% and is reduced to about 18%.
- the element reflectivity difference in light with a wavelength of 450 nm to 750 nm is within 30%. It becomes possible to implement
- the difference between the maximum value and the minimum value of the element reflectivity is about 29% to about Decrease 11 points or more down to 18%.
- the thickness of the light emitting unit 14 is adjusted. It is considered that the difference in element reflectivity can be reduced. For this reason, the difference in element reflectivity in light having a wavelength of 450 nm to 750 nm can be set to 30%.
- the element reflectance difference in light having a wavelength of 450 nm to 750 nm can be set to 30% by adjusting the thickness of the light emitting unit 14. Further, by adjusting the thickness of the light emitting unit 14 and increasing the reflectivity of the reflective electrode 15, even if the thickness of the transparent electrode 13 is increased to about 15 nm, the difference in element reflectivity in light with a wavelength of 450 nm to 750 nm can be obtained. It can be 30%.
- the thickness of the transparent electrode 13 is reduced to lower the reflectivity.
- the reflectance of the reflective electrode 15 is reduced by reducing the reflectance by reducing the thickness of the transparent electrode 13. Even in the configuration in which the drop is reduced, it is possible to realize a configuration in which the difference in element reflectivity in light with a wavelength of 450 nm to 750 nm is within 30%.
- the reflectance of the reflective electrode 15 is increased using silver or the like, even if the thickness of the transparent electrode 13 is increased to increase the reflectance, the element reflectance difference in light with a wavelength of 450 nm to 750 nm is 30. It becomes possible to realize a configuration that is within%.
- the light emitting unit 14 has a plurality of light emitting layers, such as a so-called tandem structure or a stack structure, the total thickness of the light emitting units formed between the transparent electrode 13 and the reflective electrode 15 is as described above. Thus, it is preferable that the thickness is designed so as not to interfere with a specific wavelength. Moreover, in the said structure, it is preferable that the intermediate
- the intermediate layer for example, aluminum, calcium, lithium, or the like is used and the thickness is set to about 1 nm, so that the reflectance can be reduced and the light transmission characteristics can be improved. In particular, by using calcium, lithium, or the like, it is possible to reduce reflectance and improve light transmission characteristics.
- the multiple reflection in the organic EL element 10 can be suppressed by adopting a configuration in which a metal intermediate layer is not provided.
- a metal intermediate layer for example, by providing a layer (charge generation layer) for generating electric charges in which an n-type electron transport layer and a p-type hole transport layer are stacked between a plurality of stacked light emitting layers, an intermediate layer made of metal It can be set as the structure which does not provide.
- a layer charge generation layer
- an intermediate layer made of metal It can be set as the structure which does not provide.
- the light emitting unit 14 is mainly formed of an organic material.
- the light emitting unit 14 is preferably made of a material that has little light absorption and hardly interferes with a specific wavelength.
- a material having absorption at a specific wavelength, a colored material, or the like is used, the wavelength dependency of the organic EL element 10 is increased. For this reason, it is preferable that the light emitting unit 14 itself has little attenuation and absorption of light.
- the thickness of the light emitting unit 14 tends to be large, such as a tandem structure, it is preferable that attenuation and absorption in the light emitting unit 14 are particularly small, and there is almost no attenuation or absorption at a specific wavelength. Is more preferable.
- the light extraction efficiency can be increased and the viewing angle dependency can be reduced.
- the efficiency improvement range becomes larger compared to an organic EL element exceeding 30%.
- the width of the viewing angle dependency is also increased.
- an optical member for increasing the light extraction efficiency may be provided on the light extraction side of the organic EL element.
- the substrate 11 that can be used in the organic EL element 10 is not particularly limited in the type such as glass and plastic, and may be transparent or opaque. When light is extracted from the substrate 11 side, the substrate 11 is preferably transparent. Examples of the transparent substrate 11 preferably used include glass, quartz, and a transparent resin film. A particularly preferable substrate 11 is a resin film that can give flexibility to the organic EL element 10.
- polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfone , Polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylates, cyclone resins such as Arton (trade name, manufactured by JSR) or Appel (trade name
- a barrier film made of an inorganic film, an organic film, or a hybrid film of both may be formed on the surface of the resin film.
- the barrier film had a water vapor transmission rate (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) of 0.01 g / (m 2 ⁇ 24 h) measured by a method according to JIS K 7129-1992.
- the following barrier films are preferred.
- the oxygen permeability measured by a method according to JIS K 7126-1987 is 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ atm) or less, and the water vapor permeability is 10 ⁇ 5 g / (m 2 ⁇ 24h)
- the following high-barrier film is preferable.
- the material for forming the barrier film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
- silicon oxide, silicon dioxide, silicon nitride, or the like can be used.
- the method for forming the barrier film is not particularly limited.
- the vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma weight A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.
- an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is preferable.
- the nitrogen-containing layer 12 is a layer formed adjacent to the transparent electrode 13 and sandwiched between the substrate 11 and the transparent electrode 13.
- the interaction between the silver that is the main component of the transparent electrode 13 and the compound containing the nitrogen atom that constitutes the nitrogen-containing layer 12 causes a nitrogen-containing layer.
- the diffusion distance of silver atoms on the surface is reduced, and aggregation of silver is suppressed.
- a thin silver layer that tends to be isolated in an island shape due to growth by a nuclear growth type (Volumer-Weber: VW type) is transformed into a single layer growth type (Frank-van der Merwe: FM type) It is formed. Therefore, by forming the transparent electrode 13 mainly composed of silver in contact with the nitrogen-containing layer 12, the transparent electrode 13 having a uniform thickness can be obtained although it is thin.
- the nitrogen-containing layer 12 preferably has a thickness of 5 nm or less. This is because the light transmittance increases as the thickness of the nitrogen-containing layer 12 decreases, that is, as the distance between the substrate 11 and the transparent electrode 13 decreases.
- the thickness of the nitrogen-containing layer 12 is a thickness that does not hinder the growth of the transparent electrode 13 formed on the nitrogen-containing layer 12 in the FM type, that is, the transparent electrode 13 does not have an island shape and the substrate 11 The thickness is such that it is formed as a continuous layer to cover.
- the nitrogen-containing layer 12 is a layer provided adjacent to the transparent electrode 13 and is configured using a compound containing a nitrogen atom (N).
- a compound containing a nitrogen atom (N) an unshared electron pair of nitrogen atoms that is stably bonded to silver which is the main material constituting the transparent electrode 13 is referred to as an “effective unshared electron pair”.
- the compound which comprises the nitrogen containing layer 12 is characterized by the content rate of [effective unshared electron pair] being a predetermined range.
- [effective unshared electron pair] is an unshared electron pair that is not involved in aromaticity and is not coordinated to a metal among the unshared electron pairs of nitrogen atoms contained in the compound.
- [Effective unshared electron pair] means that the unshared electron pair possessed by the nitrogen atom is aromatic regardless of whether or not the nitrogen atom itself comprising the unshared electron pair is a heteroatom constituting the aromatic ring. It depends on whether you are involved or not. For example, even if a nitrogen atom is a heteroatom constituting an aromatic ring, if the lone pair of the nitrogen atom is a lone pair that does not directly participate as an essential element in aromaticity, The shared electron pair is counted as one of [effective unshared electron pairs].
- the nitrogen atom is a Group 15 element and has 5 electrons in the outermost shell. Of these, three unpaired electrons are used for covalent bonds with other atoms, and the remaining two become a pair of unshared electron pairs. For this reason, the number of bonds of nitrogen atoms is usually three.
- R 1 and R 2 are each a hydrogen atom (H) or a substituent.
- the non-shared electron pair of the nitrogen atom constituting these groups does not participate in aromaticity and is not coordinated to the metal, and thus corresponds to [effective unshared electron pair].
- the unshared electron pair possessed by the nitrogen atom of the nitro group (—NO 2 ) is used for the resonance structure with the oxygen atom, but has a good effect as shown in the following examples. Therefore, it is considered that it exists on nitrogen as an [effective unshared electron pair] that is not involved in aromaticity and coordinated to a metal.
- FIG. 7 shows the structural formula of tetrabutylammonium chloride (TBAC) and the structural formula of tris (2-phenylpyridine) iridium (III) [Ir (ppy) 3 ].
- TBAC is a quaternary ammonium salt in which one of four butyl groups is ionically bonded to a nitrogen atom and has a chloride ion as a counter ion.
- one of the electrons constituting the unshared electron pair of the nitrogen atom is donated to the ionic bond with the butyl group.
- the nitrogen atom of TBAC is equivalent to the absence of an unshared electron pair in the first place. Therefore, the non-shared electron pair of the nitrogen atom constituting TBAC does not correspond to the [effective unshared electron pair] that is not involved in aromaticity and coordinated to the metal.
- Ir (ppy) 3 is a neutral metal complex in which an iridium atom and a nitrogen atom are coordinated.
- the unshared electron pair of the nitrogen atom constituting this Ir (ppy) 3 is coordinated to the iridium atom, and is utilized for coordination bonding. Therefore, the unshared electron pair of the nitrogen atom constituting Ir (ppy) 3 does not correspond to the [effective unshared electron pair] that is not involved in aromaticity and coordinated to the metal.
- nitrogen atoms are common as heteroatoms that can constitute an aromatic ring, and can contribute to the expression of aromaticity.
- nitrogen-containing aromatic ring examples include pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring and the like.
- FIG. 8 is a diagram showing the structural formula and molecular orbital of a pyridine ring, which is one of the nitrogen-containing aromatic rings.
- the unshared electron pair of the nitrogen atom constituting the pyridine ring corresponds to an [effective unshared electron pair] that is not involved in aromaticity and coordinated to the metal.
- FIG. 9 shows the structural formula and molecular orbitals of the pyrrole ring.
- the pyrrole ring has a structure in which one of the carbon atoms constituting the five-membered ring is substituted with a nitrogen atom, and the number of ⁇ electrons is six. Nitrogen aromatic ring. Since the nitrogen atom of the pyrrole ring is also bonded to a hydrogen atom, an unshared electron pair is mobilized to the 6 ⁇ electron system.
- this unshared electron pair is used as an essential element for the expression of aromaticity, and therefore does not participate in aromaticity and is a metal. It does not fall under [Effective unshared electron pairs] that are not coordinated to.
- FIG. 10 is a diagram showing the structural formula and molecular orbitals of the imidazole ring.
- the imidazole ring has a structure in which two nitrogen atoms N 1 and N 2 are substituted at the 1- and 3-positions in a 5-membered ring, and also contains 6 ⁇ electrons.
- Nitrogen aromatic ring is a pyridine ring-type nitrogen atom that mobilizes only one unpaired electron to the 6 ⁇ -electron system and does not utilize the unshared electron pair for aromatic expression. For this reason, the unshared electron pair of the nitrogen atom N 1 corresponds to [effective unshared electron pair].
- the unshared electron pair of the nitrogen atom N 2 is [effective Does not fall under [Unshared electron pair].
- FIG. 11 shows the structural formula and molecular orbital of the ⁇ -carboline ring.
- the ⁇ -carboline ring is a condensed ring compound having a nitrogen-containing aromatic ring skeleton, and is an azacarbazole compound in which a benzene ring skeleton, a pyrrole ring skeleton, and a pyridine ring skeleton are condensed in this order.
- the nitrogen atom N 3 of the pyridine ring mobilizes only one unpaired electron to the ⁇ -electron system
- the nitrogen atom N 4 of the pyrrole ring mobilizes an unshared electron pair to the ⁇ -electron system.
- the total number of ⁇ electrons is an aromatic ring of 14.
- the unshared electron pair of the nitrogen atom N 3 constituting the pyridine ring corresponds to [effective unshared electron pair], but constitutes the pyrrole ring.
- unshared electron pair of the nitrogen atom N 4 which does not correspond to the enable unshared electron pair.
- the unshared electron pair of the nitrogen atom constituting the condensed ring compound is involved in the bond in the condensed ring compound, similarly to the bond in the single ring such as the pyridine ring and pyrrole ring constituting the condensed ring compound. .
- the nitrogen atom having such an [effective unshared electron pair] is preferably a nitrogen atom in the nitrogen-containing aromatic ring from the viewpoint of stability and durability. Therefore, the compound contained in the nitrogen-containing layer 12 preferably has an aromatic heterocycle having a nitrogen atom having [effective unshared electron pair] as a heteroatom.
- the number n of [effective unshared electron pairs] with respect to the molecular weight M of such a compound is defined as, for example, the effective unshared electron pair content [n / M].
- the nitrogen-containing layer 12 is characterized in that this [n / M] is composed of a compound selected such that 2.0 ⁇ 10 ⁇ 3 ⁇ [n / M].
- the nitrogen-containing layer 12 preferably has an effective unshared electron pair content [n / M] defined as described above in a range of 3.9 ⁇ 10 ⁇ 3 ⁇ [n / M]. More preferably, the range is 5 ⁇ 10 ⁇ 3 ⁇ [n / M].
- the nitrogen-containing layer 12 should just be used for the compound whose effective unshared electron pair content [n / M] is the predetermined range mentioned above, even if it is comprised only with such a compound, for example.
- such a compound and another compound may be mixed and used.
- the other compound may or may not contain a nitrogen atom, and the effective unshared electron pair content [n / M] may not be within the predetermined range described above.
- the molecular weight M of the mixed compound obtained by mixing these compounds is obtained based on, for example, the mixing ratio of the compounds. Then, an average value of the effective unshared electron pair content [n / M] is obtained from the total number n of [effective unshared electron pairs] with respect to the molecular weight M. This value is preferably within the predetermined range described above. That is, it is preferable that the effective unshared electron pair content [n / M] of the nitrogen-containing layer 12 itself is within a predetermined range.
- the nitrogen-containing layer 12 is configured using a plurality of compounds and the configuration is such that the mixing ratio (content ratio) of the compounds is different in the thickness direction, the nitrogen on the side in contact with the transparent electrode 13
- the effective unshared electron pair content [n / M] in the surface layer of the containing layer 12 may be in a predetermined range.
- Table 1 also shows the corresponding general formulas when these exemplary compounds also belong to the general formulas (1) to (8a) representing other compounds-2 described below.
- X11 in the above general formula (1) represents -N (R11)-or -O-.
- R11 and R12 each represent a hydrogen atom (H) or a substituent.
- substituents examples include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group).
- alkyl group for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group.
- cycloalkyl groups for example, cyclopentyl group, cyclohexyl group, etc.
- alkenyl groups for example, vinyl group, allyl group, etc.
- alkynyl groups for example, ethynyl group, propargyl group, etc.
- aromatic hydrocarbon groups aromatic Also referred to as aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group , Pyrenyl group, biphenylyl group), aromatic heterocyclic group (eg , Furyl group, thienyl group, pyridyl group, pyridazinyl group,
- substituents may be further substituted with the above substituents.
- a plurality of these substituents may be bonded to each other to form a ring.
- substituents those not inhibiting the interaction between the compound and silver (Ag) are preferably used, and those having nitrogen having an effective unshared electron pair described above are particularly preferably applied.
- the above description regarding the substituents is similarly applied to the substituents shown in the description of the general formulas (2) to (8a) described below.
- a compound having the structure represented by the general formula (1) as described above is preferable because it can exert a strong interaction between nitrogen in the compound and silver constituting the transparent electrode 13.
- the compound having the structure represented by the general formula (1a) is one form of the compound having the structure represented by the general formula (1), and X11 in the general formula (1) is represented by —N (R11) —. It is a compound. Such a compound is preferable because the above interaction can be expressed more strongly.
- a compound. Such a compound is preferable because the above interaction can be expressed more effectively.
- the compound having the structure represented by the general formula (1a-2) is another embodiment of the compound having the structure represented by the general formula (1a), and E103 and E106 in the general formula (1a) are represented by ⁇
- Such a compound is preferable because the number of nitrogen atoms is large and the above interaction can be expressed more strongly.
- the above general formula (2) is also a form of the general formula (1).
- Y21 represents a divalent linking group composed of an arylene group, a heteroarylene group, or a combination thereof.
- R21 represents a hydrogen atom (H) or a substituent.
- k21 and k22 represent an integer of 0 to 4, and k21 + k22 is an integer of 2 or more.
- examples of the arylene group represented by Y21 include o-phenylene group, p-phenylene group, naphthalenediyl group, anthracenediyl group, naphthacenediyl group, pyrenediyl group, naphthylnaphthalenediyl group, and biphenyldiyl.
- examples of the heteroarylene group represented by Y21 include a carbazole ring, a carboline ring, a diazacarbazole ring (also referred to as a monoazacarboline ring, and one of carbon atoms constituting the carboline ring is nitrogen.
- the ring structure is replaced by an atom), a triazole ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a quinoxaline ring, a thiophene ring, an oxadiazole ring, a dibenzofuran ring, a dibenzothiophene ring, and an indole ring.
- a carbazole ring also referred to as a monoazacarboline ring
- a triazole ring also referred to as a monoazacarboline ring
- a pyrrole ring also referred to as a monoazacarboline ring
- the divalent linking group consisting of an arylene group, heteroarylene group or a combination thereof represented by Y21
- a condensed aromatic heterocycle formed by condensation of three or more rings is preferably included, and a group derived from a dibenzofuran ring or a dibenzothiophene ring is preferable.
- a group derived from a dibenzofuran ring or a dibenzothiophene ring is preferable.
- E221 to E224 and E230 to E233 are each represented by —C (R21) ⁇ .
- E203 is represented by —C (R21) ⁇ and R21 represents a linking site, and E211 is also —C (R21).
- R21 preferably represents a linking moiety.
- the general formula (3) is also a form of the general formula (1a-2).
- E301 to E312 each represent —C (R31) ⁇
- R31 represents a hydrogen atom (H) or a substituent.
- Y31 represents a divalent linking group composed of an arylene group, a heteroarylene group, or a combination thereof.
- the general formula (4) is also a form of the general formula (1a-1).
- E401 to E414 each represent —C (R41) ⁇
- R41 represents a hydrogen atom (H) or a substituent.
- Ar41 represents a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aromatic heterocyclic ring.
- k41 represents an integer of 3 or more.
- the aromatic hydrocarbon ring includes benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene Ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen And a ring, a picene ring, a pyrene ring, a pyranthrene ring, and an anthraanthrene ring.
- These rings may further have the substituents exemplified as R11
- the aromatic heterocycle when Ar41 represents an aromatic heterocycle, the aromatic heterocycle includes a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, Triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring And azacarbazole ring.
- the azacarbazole ring refers to one in which at least one carbon atom of the benzene ring constituting the carbazole ring is replaced with a nitrogen atom. These rings may further have the substituents exemplified as R11 and R12 in the general formula (1).
- R51 represents a substituent.
- R52 represents a hydrogen atom (H) or a substituent.
- E601 to E612 each represent —C (R61) ⁇ or —N ⁇ , and R61 represents a hydrogen atom (H) or a substituent.
- Ar61 represents a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aromatic heterocyclic ring.
- the substituted or unsubstituted aromatic hydrocarbon ring or the substituted or unsubstituted aromatic heterocyclic ring represented by Ar61 includes the same as Ar41 in the general formula (4). .
- R71 to R73 each represents a hydrogen atom (H) or a substituent
- Ar71 represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
- the aromatic hydrocarbon ring or aromatic heterocycle represented by Ar71 may be the same as Ar41 in the general formula (4).
- R81 to R86 each represent a hydrogen atom (H) or a substituent.
- E801 to E803 each represent —C (R87) ⁇ or —N ⁇ , and R87 represents a hydrogen atom (H) or a substituent.
- Ar81 represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
- examples of the aromatic hydrocarbon ring or aromatic heterocycle represented by Ar81 include those similar to Ar41 in the general formula (4).
- the nitrogen-containing compound represented by the general formula (8a) is one form of the nitrogen-containing compound represented by the general formula (8), and Ar81 in the general formula (8) is a carbazole derivative.
- E804 to E811 each represent —C (R88) ⁇ or —N ⁇ , and R88 represents a hydrogen atom (H) or a substituent.
- the following compounds 1 to 166 are exemplified. Is done. These compounds are compounds containing nitrogen atoms that interact with silver constituting the transparent electrode 13. Further, these compounds are materials having an electron transport property or an electron injection property. Therefore, the nitrogen-containing layer 12 configured using these compounds is suitable as the organic EL element 10, and the nitrogen-containing layer 12 can be used as an electron transport layer or an electron injection layer in the organic EL element 10. These compounds 1 to 166 also include compounds that fall within the range of the above-mentioned effective unshared electron pair content [n / M]. If such a compound is used, the nitrogen-containing layer 12 alone is formed. It can be used as a constituent compound. Further, among these compounds 1 to 166, there are compounds that fall under the general formulas (1) to (8a) described above.
- Step 2 (Synthesis of Intermediate 2)
- Intermediate 1 (0.5 mol) was dissolved in 100 ml of DMF (dimethylformamide) at room temperature in the atmosphere, NBS (N-bromosuccinimide) (2.0 mol) was added, and the mixture was stirred overnight at room temperature. The resulting precipitate was filtered and washed with methanol, yielding intermediate 2 in 92% yield.
- Step 3 (Synthesis of Compound 5) Under a nitrogen atmosphere, intermediate 2 (0.25 mol), 2-phenylpyridine (1.0 mol), ruthenium complex [( ⁇ 6 -C 6 H 6 ) RuCl 2 ] 2 (0.05 mol), tri Phenylphosphine (0.2 mol) and potassium carbonate (12 mol) were mixed in 3 L of NMP (N-methyl-2-pyrrolidone) and stirred at 140 ° C. overnight.
- NMP N-methyl-2-pyrrolidone
- the formation method includes a method using a wet process such as a coating method, an inkjet method, a coating method, a dip method, a vapor deposition method ( Resistance heating, EB method, etc.), a method using a dry process such as a sputtering method, a CVD method, or the like. Of these, the vapor deposition method is preferably applied.
- the nitrogen-containing layer 12 is formed using a plurality of compounds
- co-evaporation in which a plurality of compounds are simultaneously supplied from a plurality of evaporation sources is applied.
- a coating method is preferably applied.
- a coating solution in which the compound is dissolved in a solvent is used.
- the solvent in which the compound is dissolved is not limited.
- a coating solution may be prepared using a solvent capable of dissolving the plurality of compounds.
- the transparent electrode 13 is thinly formed so that the difference between the maximum value and the minimum value of the element reflectivity of 450 to 750 nm of the organic EL element 10 is within 30%. It is necessary to have a configuration that does not deteriorate the light transmission characteristics.
- the transparent electrode 13 is a layer composed mainly of silver, is composed of silver or an alloy composed mainly of silver, and is a layer formed adjacent to the nitrogen-containing layer 12.
- an alloy mainly composed of silver (Ag) constituting the transparent electrode 13 is silver magnesium (AgMg), silver copper (AgCu), silver palladium (AgPd), silver palladium copper (AgPdCu), silver indium (AgIn). Etc.
- a method for forming such a transparent electrode 13 a method using a wet process such as a coating method, an ink jet method, a coating method, a dipping method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method, etc. Examples include a method using a dry process. Of these, the vapor deposition method is preferably applied.
- the transparent electrode 13 is formed on the nitrogen-containing layer 12 and is sufficiently conductive even without a high-temperature annealing treatment after the formation. It may have been subjected to a high temperature annealing treatment or the like.
- the transparent electrode 13 as described above may have a configuration in which silver or an alloy layer mainly composed of silver is divided into a plurality of layers as necessary.
- the transparent electrode 13 preferably has a thickness in the range of 4 to 15 nm. A thickness of 15 nm or less is preferable because the absorption component and reflection component of the layer are kept low and the light transmittance of the transparent electrode 13 is maintained. Further, when the thickness is 4 nm or more, the conductivity of the layer is also ensured.
- a nuclear growth type Volumer-Weber: VW type
- Frank-van der Merwe FM type
- the light emitting unit 14 is provided between the anode and the cathode, and includes at least one light emitting layer including an organic material layer having light emitting properties.
- the light emitting unit 14 may include another layer between the light emitting layer and the electrode.
- the thickness of the light emitting unit 14 needs to be adjusted so that the difference between the maximum value and the minimum value of the element reflectivity of 450 nm to 750 nm of the organic EL element 10 is within 30%. Therefore, the total thickness of the light emitting unit 14 is set so that the difference between the maximum value and the minimum value of the element reflectivity of 450 nm to 750 nm of the organic EL element 10 is within 30%, and this total thickness is set. It is necessary to adjust the thickness of each layer constituting the light emitting unit 14. Further, the thickness of each layer is adjusted so that the total thickness of the set light emitting unit 14 is satisfied and the function required for each layer constituting the light emitting unit 14 is not adversely affected.
- Typical element configurations of the organic EL element 10 include the following configurations, but are not limited thereto.
- Anode / light emitting layer / cathode (2) Anode / light emitting layer / electron transport layer / cathode (3) Anode / hole transport layer / light emitting layer / cathode (4) Anode / hole transport layer / light emitting layer / electron Transport layer / cathode (5) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (6) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode ( 7) Anode / hole injection layer / hole transport layer / (electron blocking layer /) luminescent layer / (hole blocking layer /) electron transport layer / electron injection layer / cathode
- the configuration of (7) is preferable. Although used, it is not limited to this. In the above.
- the light emitting layer is formed of a single layer or a plurality of layers.
- a non-light emitting intermediate layer may be provided between the light emitting layers.
- a hole blocking layer (hole blocking layer), an electron injection layer (cathode buffer layer), or the like may be provided between the light emitting layer and the cathode, and between the light emitting layer and the anode.
- An electron blocking layer (electron barrier layer), a hole injection layer (anode buffer layer), or the like may be provided.
- the electron transport layer is a layer having a function of transporting electrons.
- the electron transport layer includes an electron injection layer and a hole blocking layer in a broad sense.
- the electron transport layer may be composed of a plurality of layers.
- the hole transport layer is a layer having a function of transporting holes.
- the hole transport layer includes a hole injection layer and an electron blocking layer in a broad sense.
- the hole transport layer may be composed of a plurality of layers.
- the light-emitting layer used in the light-emitting unit 14 provides a field in which electrons and holes injected from the electrodes or adjacent layers are recombined to emit light via excitons.
- the light emitting portion may be within the layer of the light emitting layer or may be the interface between the light emitting layer and the adjacent layer.
- the total thickness of the light emitting layer is not particularly limited, and is determined from the viewpoint of the uniformity of the film to be formed, the voltage required for light emission, and the stability of the emission color with respect to the drive current.
- the total thickness of the light emitting layers is preferably adjusted to a range of 2 nm to 5 ⁇ m, for example, more preferably adjusted to a range of 2 nm to 500 nm, and further preferably adjusted to a range of 5 nm to 200 nm.
- the individual film thickness of the light emitting layer is preferably adjusted to a range of 2 nm to 1 ⁇ m, more preferably adjusted to a range of 2 nm to 200 nm, and further preferably adjusted to a range of 3 nm to 150 nm.
- the light emitting layer preferably contains a light emitting dopant (a light emitting dopant compound, a dopant compound, also simply referred to as a dopant) and a host compound (a matrix material, a light emitting host compound, also simply referred to as a host).
- a light emitting dopant a light emitting dopant compound, a dopant compound, also simply referred to as a dopant
- a host compound a matrix material, a light emitting host compound, also simply referred to as a host.
- Luminescent dopant As the light-emitting dopant used in the light-emitting layer, a fluorescent light-emitting dopant (also referred to as a fluorescent dopant or a fluorescent compound) and a phosphorescent dopant (also referred to as a phosphorescent dopant or a phosphorescent compound) are preferably used. Of these, at least one light emitting layer preferably contains a phosphorescent dopant.
- the concentration of the luminescent dopant in the luminescent layer can be arbitrarily determined based on the specific dopant used and the device requirements.
- the concentration of the optical dopant may be contained at a uniform concentration relative to the thickness direction of the light emitting layer, or may have an arbitrary concentration distribution.
- the light emitting layer may contain a plurality of types of light emitting dopants. For example, a combination of dopants having different structures, or a combination of a fluorescent luminescent dopant and a phosphorescent luminescent dopant may be used. Thereby, arbitrary luminescent colors can be obtained.
- the color emitted by the organic EL element 10 is shown in FIG. 4.16 on page 108 of the “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985).
- the spectral radiance meter CS-2000 Konica Minolta Sensing. It is determined by the color when the result measured by (made by Co., Ltd.) is applied to the CIE chromaticity coordinates.
- one or more light-emitting layers contain a plurality of light-emitting dopants having different emission colors and emit white light.
- the combination of light-emitting dopants that exhibit white include blue and orange, and a combination of blue, green, and red.
- the phosphorescent dopant is a compound in which light emission from an excited triplet is observed.
- the phosphorescent dopant is a compound that emits phosphorescence at room temperature (25 ° C.), and has a phosphorescence quantum yield of 0 at 25 ° C. .01 or more compounds.
- a preferable phosphorescence quantum yield is 0.1 or more.
- the phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition.
- the phosphorescence quantum yield in a solution can be measured using various solvents.
- the phosphorescence emitting dopant used for the light emitting layer should just achieve the said phosphorescence quantum yield (0.01 or more) in any solvent.
- an excited state of the host compound is generated by recombination of carriers on the host compound to which carriers are transported. It is an energy transfer type in which light is emitted from the phosphorescent dopant by transferring this energy to the phosphorescent dopant.
- the other is a carrier trap type in which a phosphorescent dopant becomes a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant is obtained. In any case, it is a condition that the excited state energy of the phosphorescent dopant is lower than the excited state energy of the host compound.
- the phosphorescent dopant can be appropriately selected from known materials generally used for the light emitting layer of the organic EL device. Specific examples of known phosphorescent dopants include compounds described in the following documents.
- a preferable phosphorescent dopant is an organometallic complex having Ir as a central metal. More preferably, a complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond is preferable.
- Phosphorescent compounds are, for example, Organic ⁇ ⁇ ⁇ Letters magazinesvol.3 No.16 2579-2581 (2001), Inorganic Chemistry, Vol.30, No.8 1685-1687. (1991), J. Am. Chem. Soc., 123 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, 704 1704-1711 (2001), Inorganic Chemistry, Vol. 41 No. 12 3055-3066 (2002), New Journal of ⁇ Chemistry., 26 1171 (2002), European Journal of Organic Chemistry, Vol.4 695-709 (2004), further described in these references Can be synthesized by applying a method such as the reference.
- the fluorescent light-emitting dopant is a compound that can emit light from an excited singlet, and is not particularly limited as long as light emission from the excited singlet is observed.
- Examples of the fluorescent light-emitting dopant include anthracene derivatives, pyrene derivatives, chrysene derivatives, fluoranthene derivatives, perylene derivatives, fluorene derivatives, arylacetylene derivatives, styrylarylene derivatives, styrylamine derivatives, arylamine derivatives, boron complexes, coumarin derivatives, Examples include pyran derivatives, cyanine derivatives, croconium derivatives, squalium derivatives, oxobenzanthracene derivatives, fluorescein derivatives, rhodamine derivatives, pyrylium derivatives, perylene derivatives, polythiophene derivatives, rare earth complex compounds, and the like.
- a light emitting dopant using delayed fluorescence may be used as the fluorescent light emitting dopant.
- the luminescent dopant using delayed fluorescence include compounds described in, for example, International Publication No. 2011/156793, Japanese Patent Application Laid-Open No. 2011-213643, Japanese Patent Application Laid-Open No. 2010-93181, and the like.
- the host compound is a compound mainly responsible for charge injection and transport in the light emitting layer, and its own light emission is not substantially observed in the organic EL element.
- it is a compound having a phosphorescence quantum yield of phosphorescence of less than 0.1 at room temperature (25 ° C.), more preferably a compound having a phosphorescence quantum yield of less than 0.01.
- the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.
- the excited state energy of a host compound is higher than the excited state energy of the light emission dopant contained in the same layer.
- a host compound may be used independently or may be used in combination of multiple types. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element 10 can be highly efficient.
- the compound conventionally used by the organic EL element can be used.
- it may be a low molecular compound, a high molecular compound having a repeating unit, or a compound having a reactive group such as a vinyl group or an epoxy group.
- Tg glass transition temperature
- the glass transition point (Tg) is a value obtained by a method based on JIS-K-7121 using DSC (Differential Scanning Calorimetry).
- host compounds include, but are not limited to, compounds described in the following documents. JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No.
- the electron transport layer used for the organic EL element 10 is made of a material having a function of transporting electrons, and has a function of transmitting electrons injected from the cathode to the light emitting layer.
- the electron transport material may be used alone or in combination of two or more.
- the total thickness of the electron transport layer is not particularly limited, but is usually in the range of 2 nm to 5 ⁇ m, more preferably 2 nm to 500 nm, and further preferably 5 nm to 200 nm.
- the total thickness of the light emitting unit 14 is set so that the difference between the maximum value and the minimum value of the element reflectivity of 450 nm to 750 nm is within 30%.
- the total thickness of the light emitting unit 14 is preferably adjusted by appropriately adjusting the total thickness of the electron transport layer between several nanometers and several micrometers.
- the electron mobility of the electron transport layer is preferably 10 -5 cm 2 / Vs or more .
- the material used for the electron transport layer may have any of the electron injection property or the transport property or the hole barrier property. Any one can be selected and used. Examples thereof include nitrogen-containing aromatic heterocyclic derivatives, aromatic hydrocarbon ring derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, silole derivatives, and the like.
- nitrogen-containing aromatic heterocyclic derivatives examples include carbazole derivatives, azacarbazole derivatives (one or more carbon atoms constituting the carbazole ring are substituted with nitrogen atoms), pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, pyridazine derivatives, triazine derivatives.
- aromatic hydrocarbon ring derivative examples include naphthalene derivatives, anthracene derivatives, triphenylene and the like.
- a metal complex having a quinolinol skeleton or a dibenzoquinolinol skeleton as a ligand such as tris (8-quinolinol) aluminum (Alq3), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7- Dibromo-8-quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and metal complexes thereof
- a metal complex in which the central metal is replaced with In, Mg, Cu, Ca, Sn, Ga, or Pb can also be used as an electron transporting material.
- metal-free or metal phthalocyanine, or those having the terminal substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material.
- the distyrylpyrazine derivative exemplified as the material for the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.
- a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
- a doping material may be doped into the electron transport layer as a guest material to form an electron transport layer having a high n property (electron rich).
- the doping material include metal compounds such as metal complexes and metal halides, and other n-type dopants.
- Specific examples of the electron transport layer having such a structure include, for example, JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J. Appl. Phys., 95, 5773 (2004) and the like.
- preferable electron transport materials include, but are not limited to, compounds described in the following documents.
- More preferable electron transport materials include pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, carbazole derivatives, azacarbazole derivatives, and benzimidazole derivatives.
- the hole blocking layer is a layer having a function of an electron transport layer in a broad sense. Preferably, it is made of a material having a function of transporting electrons and a small ability to transport holes. By blocking holes while transporting electrons, the recombination probability of electrons and holes can be improved. Moreover, the structure of the above-mentioned electron carrying layer can be used as a hole-blocking layer as needed.
- the hole blocking layer provided in the organic EL element 10 is preferably provided adjacent to the cathode side of the light emitting layer.
- the thickness of the hole blocking layer is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.
- the material used for the hole blocking layer the material used for the above-described electron transport layer is preferably used, and the material used as the above-described host compound is also preferably used for the hole blocking layer.
- the electron injection layer (also referred to as “cathode buffer layer”) is a layer provided between the cathode and the light emitting layer in order to lower the driving voltage and improve the light emission luminance.
- An example of an electron injection layer can be found in the second chapter, Chapter 2, “Electrode Materials” (pages 123-166) of “Organic EL devices and their industrialization front line (issued by NTT Corporation on November 30, 1998)”. Are listed.
- the electron injection layer is provided as necessary, and is provided between the cathode and the light emitting layer or between the cathode and the electron transport layer as described above.
- the electron injection layer is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 nm, depending on the material.
- membrane in which a constituent material exists intermittently may be sufficient.
- JP-A-6-325871, JP-A-9-17574, and JP-A-10-74586 Specific examples of materials preferably used for the electron injection layer include metals typified by strontium and aluminum, alkali metal compounds typified by lithium fluoride, sodium fluoride, and potassium fluoride, magnesium fluoride, and fluoride. Examples thereof include alkaline earth metal compounds typified by calcium, metal oxides typified by aluminum oxide, metal complexes typified by lithium 8-hydroxyquinolate (Liq), and the like.
- the material used for said electron injection layer may be used independently, and may be used in combination of multiple types.
- the hole transport layer is made of a material having a function of transporting holes.
- the hole transport layer is a layer having a function of transmitting holes injected from the anode to the light emitting layer.
- the total thickness of the hole transport layer is not particularly limited, but is usually in the range of 5 nm to 5 ⁇ m, more preferably 2 nm to 500 nm, and further preferably 5 nm to 200 nm.
- the material used for the hole transport layer may have any of a hole injection property or a transport property and an electron barrier property.
- a hole transport material an arbitrary material can be selected and used from conventionally known compounds.
- the hole transport material may be used alone or in combination of two or more.
- Hole transport materials include, for example, porphyrin derivatives, phthalocyanine derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, hydrazone derivatives, stilbene derivatives, polyarylalkane derivatives, tria Reelamine derivatives, carbazole derivatives, indolocarbazole derivatives, isoindole derivatives, acene derivatives such as anthracene and naphthalene, fluorene derivatives, fluorenone derivatives, polyvinyl carbazole, polymer materials having aromatic amine introduced in the main chain or side chain, or Oligomer, polysilane, conductive polymer or oligomer (eg, PEDOT: PSS, aniline copolymer, polyaniline, polythiophene, etc.) And the like.
- PEDOT PEDOT: PS
- triarylamine derivatives examples include a benzidine type typified by ⁇ -NPD, a starburst type typified by MTDATA, and a compound having fluorene or anthracene in the triarylamine linking core part.
- hexaazatriphenylene derivatives described in JP-T-2003-519432 and JP-A-2006-135145 can also be used as the hole transport material.
- a hole transport layer having a high p property doped with impurities can also be used.
- the configurations described in JP-A-4-297076, JP-A-2000-196140, 2001-102175, J. Appl. Phys., 95, 5773 (2004), etc. can also be applied to the transport layer.
- so-called p-type hole transport materials and p-type materials as described in JP-A-11-251067 and J. Huang et.al. (Applied Physics Letters 80 (2002), p. 139).
- Inorganic compounds such as -Si and p-type -SiC can also be used.
- ortho-metalated organometallic complexes having Ir or Pt as the central metal as typified by Ir (ppy) 3 are also preferably used.
- the hole transport material a triarylamine derivative, a carbazole derivative, an indolocarbazole derivative, an azatriphenylene derivative, an organometallic complex, or an aromatic amine is introduced into the main chain or side chain.
- the polymer materials or oligomers used are preferably used.
- Specific examples of the hole transport material include, but are not limited to, the compounds described in the following documents in addition to the documents listed above. Appl. Phys. Lett. 69, 2160 (1996), J. Lumin. 72-74, 985 (1997), Appl. Phys. Lett. 78, 673 (2001), Appl. Phys. Lett. 90, 183503 (2007) ), Appl.
- the electron blocking layer is a layer having a function of a hole transport layer in a broad sense. Preferably, it is made of a material having a function of transporting holes and a small ability to transport electrons.
- the electron blocking layer can improve the probability of recombination of electrons and holes by blocking electrons while transporting holes.
- the structure of the above-mentioned hole transport layer can be used as an electron blocking layer of the organic EL element 10 as necessary.
- the electron blocking layer provided in the organic EL element 10 is preferably provided adjacent to the anode side of the light emitting layer.
- the thickness of the electron blocking layer is preferably in the range of 3 to 100 nm, and more preferably in the range of 5 to 30 nm.
- the materials used for the electron blocking layer can be preferably used.
- the material used as the above-mentioned host compound can also be preferably used as the electron blocking layer.
- the hole injection layer (also referred to as “anode buffer layer”) is a layer provided between the anode and the light emitting layer in order to lower the driving voltage and improve the light emission luminance.
- An example of the hole injection layer is “Organic EL device and its industrialization front line (November 30, 1998, issued by NTT)”, Chapter 2, Chapter 2, “Electrode material” (pages 123-166). It is described in.
- the hole injection layer is provided as necessary, and is provided between the anode and the light emitting layer or between the anode and the hole transport layer as described above.
- Examples of the material used for the hole injection layer include the materials used for the hole transport layer described above. Among them, phthalocyanine derivatives typified by copper phthalocyanine, hexaazatriphenylene derivatives as described in JP-T-2003-519432, JP-A-2006-135145, etc., metal oxides typified by vanadium oxide, amorphous Conductive polymers such as carbon, polyaniline (emeraldine) and polythiophene, orthometalated complexes represented by tris (2-phenylpyridine) iridium complex, and triarylamine derivatives are preferred.
- the materials used for the hole injection layer described above may be used alone or in combination of two or more.
- the light emitting unit 14 constituting the organic EL element 10 may further include other inclusions.
- the inclusion include halogen elements such as bromine, iodine, and chlorine, halogenated compounds, alkali metals such as Pd, Ca, and Na, alkaline earth metals, transition metal compounds, complexes, and salts.
- the content of the inclusion can be arbitrarily determined, but is preferably 1000 ppm or less, more preferably 500 ppm or less, and even more preferably 50 ppm or less with respect to the total mass% of the contained layer. . However, it is not within this range depending on the purpose of improving the transportability of electrons and holes or the purpose of favoring the exciton energy transfer.
- a method for forming the light emitting unit 14 (hole injection layer, hole transport layer, light emitting layer, hole blocking layer, electron transport layer, electron injection layer, etc.) of the organic EL element 10 will be described.
- Examples of the wet method include a spin coating method, a casting method, an ink jet method, a printing method, a die coating method, a blade coating method, a roll coating method, a spray coating method, a curtain coating method, and an LB method (Langmuir-Blodgett method).
- a method having high suitability for a roll-to-roll method such as a die coating method, a roll coating method, an ink jet method, or a spray coating method is preferable.
- examples of the liquid medium for dissolving or dispersing the material of the light emitting unit 14 include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, and the like.
- Aromatic hydrocarbons such as mesitylene and cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin and dodecane, and organic solvents such as DMF and DMSO can be used.
- it can disperse
- the vapor deposition conditions vary depending on the type of compound used, etc., but generally the boat heating temperature is 50 ° C. to 450 ° C., and the vacuum is 10 ⁇ 6 Pa to 10 ⁇ . It is desirable to appropriately select 2 Pa, a deposition rate of 0.01 nm / second to 50 nm / second, a substrate temperature of ⁇ 50 ° C. to 300 ° C., and a film thickness of 0.1 nm to 5 ⁇ m, preferably 5 nm to 200 nm.
- the formation of the organic EL element 10 is preferably made consistently from the light emitting unit 14 to the reflective electrode 15 by a single evacuation, but it may be taken out halfway and subjected to different film forming methods. In that case, it is preferable to perform the work in a dry inert gas atmosphere. Different formation methods may be applied for each layer.
- the reflective electrode 15 needs to be made of a highly reflective material so that the difference between the maximum value and the minimum value of the element reflectivity of 450 nm to 750 nm of the organic EL element 10 is within 30%. . Furthermore, it is necessary that the surface has high uniformity and flatness so as not to interfere with a specific wavelength of reflected light.
- an electrode substance made of a metal referred to as an electron injecting metal
- an alloy referred to as an electron injecting metal
- an alloy referred to as an electrically conductive compound
- Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, aluminum, silver, silver-based alloys, aluminum / silver mixtures, rare earth metals, and the like.
- the reflective electrode 15 preferably has a structure containing aluminum or silver on the surface on the light emitting unit 14 side particularly because of its high reflectance.
- the reflective electrode 15 can have a laminated structure of silver and aluminum by forming aluminum of about 1 nm between silver and the light emitting unit.
- the reflective electrode 15 can be produced by using the above electrode material using a method such as vapor deposition or sputtering.
- the sheet resistance of the reflective electrode 15 is several hundred ⁇ / sq. The following is preferred.
- the thickness of the reflective electrode 15 is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 nm to 200 nm.
- the above-described effective unshared electron pair content ratio [ A nitrogen-containing layer containing a compound in which n / M] is 2.0 ⁇ 10 ⁇ 3 ⁇ [n / M] is preferably formed as an electron transporting layer.
- a nitrogen-containing layer containing a compound in which n / M] is 2.0 ⁇ 10 ⁇ 3 ⁇ [n / M] is preferably formed as an electron transporting layer.
- the light scattering layer is preferably a high refractive index layer having a refractive index within a range of 1.7 or more and less than 2.5 at a wavelength of 550 nm.
- Waveguide mode light confined in the light emitting layer of the organic light emitting element and plasmon mode light reflected from the reflecting electrode are light of a specific optical mode, and in order to extract such light, the refractive index is at least 1.7 or more. is required.
- the higher-order mode of the plasmon mode there is almost no light in a region with a refractive index of 2.5 or higher, and the amount of light that can be extracted does not increase even with a refractive index higher than this.
- the light scattering layer may be formed of a single material having a refractive index of 1.7 or more and less than 2.5, or mixed with two or more compounds to have a refractive index of 1.7 or more and less than 2.5.
- a film may be formed.
- the refractive index of the light scattering layer can be substituted by a calculated refractive index calculated by a total value obtained by multiplying the refractive index specific to each material by the mixing ratio.
- the refractive index of each material may be less than 1.7 or 2.5 or more, and it is sufficient that the mixed film has a refractive index of 1.7 or more and less than 2.5.
- the refractive index can be measured with a multiwavelength Abbe refractometer, a prism coupler, a Mickelson interferometer, a spectroscopic ellipsometer, or the like.
- the light scattering layer may be a mixed scattering layer (scattering film) using a difference in refractive index due to a mixture of resin and particles, or may be a shape control scattering layer formed by shape control of an uneven structure or the like.
- the light scattering layer is a layer that improves light extraction efficiency, and preferably has a transmittance of 50% or more, more preferably 55% or more, and particularly preferably 60% or more.
- FIG. 12 the cross-sectional schematic diagram of the organic electroluminescent element (organic EL element) of this embodiment is shown.
- the organic EL element 20 has a so-called tandem structure in which light emitting units are stacked.
- the organic EL element 20 includes a substrate 21, a nitrogen-containing layer 22 provided on the substrate 21, a transparent electrode 23 formed in contact with the nitrogen-containing layer 22, a first light emitting unit 24 provided on the transparent electrode 23, The intermediate layer 25 provided on the first light emitting unit 24, the second light emitting unit 26 provided on the first light emitting unit 24 via the intermediate layer 25, and the reflective electrode 27 provided on the second light emitting unit 26 Is provided.
- the substrate 21, the nitrogen-containing layer 22, the transparent electrode 23, and the reflective electrode 27 can have the same configuration as that in the first embodiment described above. Further, in the organic EL element 20, the total thickness of the first light emitting unit 24, the intermediate layer 25, and the second light emitting unit 26 formed between the transparent electrode 23 and the reflective electrode 27 is the above-described first thickness. This corresponds to the thickness of the light emitting unit in the organic EL element of one embodiment. Therefore, in the organic EL element 20, the total thickness of the transparent electrode 23, the reflective electrode 27, the first light emitting unit 24, the intermediate layer 25, and the second light emitting unit 26 is an element in light with a wavelength of 450 nm to 750 nm. In order to reduce the difference between the maximum value and the minimum value of the reflectance to within 30%, it is necessary to perform optimization similar to the first embodiment. Since the method of optimizing these configurations is the same as that in the first embodiment described above, description thereof is omitted.
- the total thickness of the first light-emitting unit 24 and the second light-emitting unit 26 may be optimized so that the difference in element reflectivity in light with a wavelength of 450 nm to 750 nm is within 30%.
- the thickness is not particularly limited. However, considering that the reflection by the intermediate layer 25 affects the element reflectivity, the first light-emitting unit 24 and the second light-emitting unit 26 have a total thickness, and the difference in element reflectivity in light with a wavelength of 450 nm to 750 nm. It is preferable that the thickness of the first light emitting unit 24 and the thickness of the second light emitting unit 26 are optimized by simulation while being optimized to be within 30%.
- the first light emitting unit 24 and the second light emitting unit are set so that the difference between the maximum value and the minimum value of the element reflectivity in light having a wavelength of 450 nm to 750 nm is within 30%.
- the total thickness 26 and the material of the intermediate layer 25 need to be set.
- tandem structure As typical element configurations of the tandem structure, for example, the following configurations can be given. (1) Anode / first light emitting unit / intermediate layer / second light emitting unit / cathode (2) anode / first light emitting unit / intermediate layer / second light emitting unit / intermediate layer / third light emitting unit / cathode The first light emitting unit, the second light emitting unit, and the third light emitting unit may all be the same or different. Two light emitting units may be the same, and the remaining one may be different. Each light emitting unit can have the same configuration as in the first embodiment.
- each light emitting unit may be laminated directly or via an intermediate layer.
- the intermediate layer is composed of, for example, an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, or an intermediate insulating layer, and the electrons are positively connected to the adjacent layer on the anode side and positive to the adjacent layer on the cathode side.
- a known material configuration can be used as long as the layer has a function of supplying holes.
- tandem organic EL element examples include, for example, US Pat. No. 6,337,492, US Pat. No. 7,420,203, US Pat. No. 7,473,923, US Pat. No. 6,872, No. 472, US Pat. No. 6,107,734, US Pat. No. 6,337,492, International Publication No. 2005/009087, JP-A 2006-228712, JP-A 2006-24791, JP-A 2006 -49393, JP-A-2006-49394, JP-A-2006-49396, JP-A-2011-96679, JP-A-2005-340187, JP-A-4711424, JP-A-34966681, and JP-A-3884564 No. 4, Japanese Patent No.
- JP-A-2008-078414 JP-A-2007-059848, JP-A-2003-272860, JP-A-2003-045676, WO 2005/094130, etc. However, it is not limited to these.
- the intermediate layer 25 is preferably a layer having a low reflectance and an excellent light transmission property, like the transparent electrode 23. Due to the low reflectance and high transparency, the multiple reflection between the intermediate layer 25 and the reflective electrode 27, and the intermediate layer 25 and the transparent electrode 23 is suppressed, and the wavelength dependence of the light extracted from the organic EL element 20, The viewing angle dependency can be suppressed.
- the intermediate layer 25 having a tandem structure for example, ITO (indium / tin oxide), IZO (indium / zinc oxide), ZnO 2 , TiN, ZrN, HfN, TiO X , VO X , CuI, InN, GaN, CuAlO 2 , CuGaO 2 , SrCu 2 O 2 , LaB 6 , RuO 2 , Al, etc., a two-layer film such as Au / Bi 2 O 3 , SnO 2 / Multilayer films such as Ag / SnO 2 , ZnO / Ag / ZnO, Bi 2 O 3 / Au / Bi 2 O 3 , TiO 2 / TiN / TiO 2 , TiO 2 / ZrN / TiO 2 , and fullerenes such as C60, Conductive organic material layers such as oligothiophene, conductive organic materials such as metal phthalocyanines, metal-free phthal
- the intermediate layer 25 is made of, for example, aluminum, calcium, lithium, etc., and has a thickness of about 1 nm. It is preferable to form by. By forming the intermediate layer 25 thin with these materials, the reflectance can be reduced and the light transmission characteristics can be improved. In particular, by using calcium, lithium, or the like, it is possible to reduce reflectance and improve light transmission characteristics.
- FIG. 13 the cross-sectional schematic diagram of the organic electroluminescent element (organic EL element) of a modification is shown.
- the organic EL element 20A has a configuration in which an intermediate layer is omitted from the tandem structure of the organic EL element of the second embodiment described above.
- the organic EL element 20A has the same configuration as the organic EL element 20 of the second embodiment shown in FIG. 12 except that it does not have an intermediate layer. For this reason, the description about each layer which comprises the organic EL element 20A is abbreviate
- middle layer can suppress the multiple reflection in the organic EL element 20A.
- an intermediate layer is not provided by providing a charge generation layer in which an n-type electron transport layer and a p-type hole transport layer are stacked between a plurality of stacked light-emitting layers. it can. With this configuration, multiple reflections between the reflective electrode 27 and the transparent electrode 23 and the intermediate layer can be eliminated, and the wavelength dependency and viewing angle dependency of light extracted from the organic EL element 20A can be suppressed.
- the difference in element reflectivity in light having a wavelength of 450 nm to 750 nm tends to be smaller than that of the organic EL element according to the second embodiment having an intermediate layer for the reasons described above. Therefore, it is possible to further improve the wavelength dependency and viewing angle dependency of light extracted from the organic EL element 20A.
- the intermediate layer is not provided in the tandem structure, it is not necessary to consider the reflection by the intermediate layer. Therefore, the total thickness of the first light emitting unit 24 and the second light emitting unit 26 is an element for light with a wavelength of 450 nm to 750 nm. What is necessary is just to optimize so that a reflectance difference may be within 30%, and the thickness of each layer is not specifically limited.
- the intermediate layer is not provided in the tandem structure, it is necessary to have a configuration in which charges are generated in the layer that forms the interface between the first light emitting unit 24 and the second light emitting unit 26. That is, the first light emitting unit 24 layer (uppermost layer) in contact with the second light emitting unit 26 and the second light emitting unit 26 layer (lowermost layer) in contact with the first light emitting unit 24 generate electric charges. There is a need. For example, by forming an n-type electron transport layer in the uppermost layer of the first light-emitting unit 24 and forming a p-type hole transport layer in the lowermost layer of the second light-emitting unit 26, The structure is such that charge can be generated at the interface with the two light emitting units 26.
- n-type electron transport layer for example, an n-type impurity (electron rich) electron transport layer doped with an n-type impurity as a guest material can be used.
- the doping material include metal compounds such as metal complexes and metal halides, and other n-type dopants.
- p-type hole transport layer for example, a p-type impurity (hole-rich) hole transport layer can be used by doping a p-type impurity as a guest material.
- p-type hole transport materials inorganic compounds such as p-type-Si and p-type-SiC can also be used.
- the transparent support substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus.
- Each of the vapor deposition crucibles in the vacuum vapor deposition apparatus was filled with the constituent material of each layer of the organic EL element in an amount optimal for element fabrication.
- the evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.
- the deposition crucible containing Compound U-1 was energized and heated, and deposited on a transparent support substrate at a deposition rate of 0.1 nm / second. A stratum was formed. Next, 8 nm of silver was vapor-deposited at 0.3 nm / second on the formed underlayer to form an anode.
- a vapor deposition crucible containing compound M-2 is energized and heated on the formed anode, vapor-deposited on a transparent support substrate at a vapor deposition rate of 0.1 nm / second, and a hole injection transport layer having a film thickness of 120 nm. Formed.
- Compound BD-1 and Compound H-1 are co-evaporated at a deposition rate of 0.1 nm / second so that the concentration of Compound BD-1 is 5%, and a fluorescent light emitting layer exhibiting blue light emission with a film thickness of 30 nm Formed. Further, compounds GD-1, RD-1 and compound H-2 were co-deposited at a deposition rate of 0.1 nm / second so that the concentration of compound GD-1 was 17% and RD-1 was 0.8%. A phosphorescent light emitting layer having a film thickness of 15 nm and exhibiting yellow was formed.
- Compound E-0 was deposited at a deposition rate of 0.1 nm / second to form a hole blocking layer having a thickness of 5 nm.
- Compound E-1 was co-evaporated at a deposition rate of 0.1 nm / second and potassium fluoride (KF) was deposited at a deposition rate of 0.01 nm / second to form an electron transport layer having a thickness of 80 nm.
- KF potassium fluoride
- cathode aluminum was vapor-deposited on the electron transport layer of the formed light emitting unit to form a cathode having a thickness of 100 nm.
- Table 2 below shows the configurations of the samples 101 to 112 and the measurement results of the element reflectance difference, element efficiency, and viewing angle dependency. Note that the quantum efficiency and viewing angle dependency are shown as relative values from the sample 101.
- each organic EL element of Samples 201 to 212 was fabricated and evaluated. As shown in Table 3, each of the organic EL elements of Samples 201 to 212 was adjusted by changing the thickness of the light-emitting unit by adjusting the thickness of the hole injecting and transporting layer. It was produced using the same method. And the element reflectance difference, element efficiency, and viewing angle dependence were measured by the same method as Example 1 described above. Note that the quantum efficiency and viewing angle dependency were obtained as relative values from the sample 101. Table 3 below shows the configurations of the samples 201 to 212 and the measurement results of the element reflectance difference, element efficiency, and viewing angle dependency.
- the thickness of the light emitting unit affects the difference in element reflectivity at each wavelength
- the difference between the maximum value and the minimum value of the element reflectivity in light with a wavelength of 450 nm to 750 nm should be 30% or less.
- Each organic EL element of Samples 301 to 322 was fabricated and evaluated.
- Samples 301 to 322 were prepared by forming the following light scattering layer on the substrate and forming the anode on the light scattering layer, and samples 101 to 112 of Example 1 and 201, It was produced using the same method as in 203-207 and 209-212.
- Table 4 shows the numbers of the samples of Example 1 and Example 2 corresponding to the configurations of the organic EL elements of Samples 301 to 322.
- the dispersion constituting the light scattering layer was spin-coated by spin coating (500 rpm, 30 seconds), then simply dried (80 ° C., 2 minutes), and further baked (120 ° C., 60 minutes), a light scattering layer having a thickness of 700 nm was formed.
- the dispersion was prepared as a light scattering layer preparation, TiO 2 particles having a refractive index of 2.4 and an average particle size of 0.25 ⁇ m (JR600A manufactured by Teika Co., Ltd.) and a resin solution (ED230AL (organic / inorganic hybrid resin) manufactured by APM).
- the formulation was designed at a ratio of 10 ml so that the solid content ratio was 70 vol% / 30 vol%, the solvent ratio of n-propyl acetate and cyclohexanone was 10 wt% / 90 wt%, and the solid concentration was 15 wt%.
- the above-mentioned TiO 2 particles and a solvent are mixed and cooled at room temperature, and then the standard of the microchip step (MS-3 MSmm 3 mm ⁇ ) is applied to an ultrasonic disperser (SMH UH-50). Dispersion was added for 10 minutes under the conditions to prepare a TiO 2 dispersion. Next, while stirring the TiO 2 dispersion at 100 rpm, the resin was mixed and added little by little. After the addition was completed, the stirring speed was increased to 500 rpm and mixed for 10 minutes to obtain a light scattering layer coating solution. Then, it filtered with the hydrophobic PVDF 0.45 micrometer filter (made by Whatman), and obtained the target dispersion liquid.
- SSH UH-50 ultrasonic disperser
- the element reflectance difference, the element efficiency improvement rate, and the viewing angle dependency were measured in the same manner as in Example 1 described above.
- the viewing angle dependency was obtained as a relative value from the sample 101.
- Table 4 below shows the configurations of the samples 301 to 322, and the measurement results of the element reflectance difference, the element efficiency improvement rate, and the viewing angle dependency.
- the sample when the difference in element reflectivity is 30%, the sample is divided into a sample having a viewing angle dependency of 25 or less and a sample of 40 or more. Specifically, the viewing angle dependence is 18 to 25 for a sample with an element reflectance difference of 30% or less, whereas the viewing angle dependence is 40 to 43 for a sample with an element reflectance difference of more than 30%. there were.
- the sample 304 with a device reflectance difference of 13% has a viewing angle dependency of 18, a sample 311 with a device reflectance difference of 19% has a viewing angle dependency of 20 and a device reflectance difference of 29%.
- the viewing angle dependency is 25, whereas in the sample 302 with the element reflectance difference of 33%, the viewing angle dependency increases to 40. That is, even if the element reflectivity difference is increased by 16 points from 13% to 29%, the viewing angle dependency is increased only from 18 to 25. On the other hand, when the element reflectivity difference changes over 30%, the viewing angle dependency increases from 25 to 40 even if the element reflectivity difference is increased by 4 points from 29% to 33%. From this result, it can be seen that when the element reflectance difference exceeds 30%, the viewing angle dependency of the organic EL element is rapidly deteriorated.
- an organic EL device having excellent viewing angle dependency is realized by setting the difference between the maximum value and the minimum value of the element reflectivity in light with a wavelength of 450 nm to 750 nm to 30% or less. be able to.
- the deposition crucible containing the compound M-2 is energized and heated on the formed anode, and deposited on a transparent support substrate at a deposition rate of 0.1 nm / second, to form a hole injection transport layer having a thickness of 120 nm. Formed.
- Compound BD-1 and Compound H-1 are co-evaporated at a deposition rate of 0.1 nm / second so that the concentration of Compound BD-1 is 5%, and a fluorescent light emitting layer exhibiting blue light emission with a film thickness of 30 nm Formed.
- Compound E-0 was deposited at a deposition rate of 0.1 nm / second to form a hole blocking layer having a thickness of 5 nm. Further, Compound E-1 was co-evaporated at a deposition rate of 0.1 nm / second and potassium fluoride (KF) of 0.01 nm / second to form an electron transport layer having a thickness of 45 nm.
- KF potassium fluoride
- Compound M-1 was deposited on the intermediate layer at a deposition rate of 0.1 nm / second to form a 15 nm-thick hole injection layer. Further, the vapor deposition crucible containing the compound M-2 was energized and heated, and vapor deposition was performed at a vapor deposition rate of 0.1 nm / second to form a hole injection transport layer having a film thickness of 120 nm.
- compounds GD-1, RD-1 and compound H-2 were co-deposited at a deposition rate of 0.1 nm / second so that the concentration of compound GD-1 was 17% and RD-1 was 0.8%. Then, a phosphorescent light emitting layer having a film thickness of 15 nm and exhibiting yellow was formed.
- Compound E-0 was deposited at a deposition rate of 0.1 nm / second to form a hole blocking layer having a thickness of 5 nm. Thereafter, Compound E-1 was co-evaporated at a deposition rate of 0.1 nm / second and potassium fluoride (KF) of 0.01 nm / second to form an electron transport layer having a thickness of 45 nm.
- KF potassium fluoride
- cathode silver was vapor-deposited on the electron transport layer of the formed light emitting unit to form a cathode having a thickness of 100 nm.
- the element reflectance difference, the element efficiency, and the viewing angle dependency were measured in the same manner as in Example 1 described above. Note that the quantum efficiency and viewing angle dependency were obtained as relative values from the sample 401. Table 5 below shows the configurations of the samples 401 to 412 and the measurement results of the element reflectance difference, element efficiency, and viewing angle dependency.
- the difference in element reflectivity is large, and the element efficiency and the viewing angle dependency are greatly reduced. This is presumably because multiple reflection through the intermediate layer occurred due to the high reflectance of Al and the low light transmittance, and the viewing angle dependency deteriorated.
- the element reflectance difference of the sample having a small film thickness is small and the element reflectance difference of the sample having a large film thickness is large. This is considered because the light transmittance of the intermediate layer is improved and the occurrence of multiple reflection through the intermediate layer can be suppressed by reducing the film thickness of the intermediate layer.
- the sample 412 having no intermediate layer had the smallest element reflectance difference, and the best results were obtained in terms of element efficiency and viewing angle dependency. From this result, it is possible to suppress multiple reflection through the intermediate layer in the organic EL element by adopting a configuration in which the reflectance of the intermediate layer is low and the light transmittance is high, and in particular, the configuration in which the intermediate layer is not provided. It is considered that the viewing angle dependency of the organic EL element can be improved.
- each organic EL element of Samples 501 to 518 was produced and evaluated. As shown in Table 6, each of the organic EL elements of Samples 501 to 518 was adjusted by changing the thickness of the first light emitting unit and the second light emitting unit by adjusting the thickness of the hole injecting and transporting layer. 4 was manufactured using the same method as Sample 4406 or Sample 412. And the element reflectance difference, element efficiency, and viewing angle dependence were measured by the same method as Example 1 described above. Note that the quantum efficiency and viewing angle dependency were obtained as relative values from the sample 401.
- Table 6 shows the configurations of the samples 501 to 518 and the measurement results of the element reflectance difference, element efficiency, and viewing angle dependency.
- the difference in element reflectivity at each wavelength is affected by the total thickness of the light emitting units. Even when the thickness of the light emitting unit affects the difference in element reflectivity at each wavelength, the difference between the maximum value and the minimum value of the element reflectivity in light having a wavelength of 450 nm to 750 nm should be 30% or less. Thus, it can be seen that an organic EL element excellent in element efficiency and viewing angle dependency can be realized.
- Each organic EL element of Samples 601 to 628 was produced and evaluated.
- Samples 601 to 628 were prepared by forming the following light scattering layer on the substrate and forming the anode on this light scattering layer, and samples 401 to 412 of Example 4 and 501 of Example 5 It was produced using the same method as 502, 504 to 511, and 513 to 518.
- the light scattering layer was formed by the same method as the sample 301 of Example 3 described above.
- Table 7 shows the numbers of the samples of Example 4 and Example 5 corresponding to the configurations of the organic EL elements of Samples 601 to 628.
- the device reflectance difference, the device efficiency improvement rate, and the viewing angle dependency were measured in the same manner as in the above-described Example 1 and Example 3.
- the viewing angle dependency was obtained as a relative value from the sample 401.
- Table 7 below shows the configurations of the samples 601 to 628 and the measurement results of the element reflectance difference, element efficiency improvement rate, and viewing angle dependency.
- the element reflectivity difference greatly changes at 30%.
- the element reflectivity difference of the sample 606 is 27% and the element reflectivity difference of the sample 607 is 31%.
- the viewing angle dependency is 15 in the sample 606, whereas the sample 607 is deteriorated to 26. ing.
- the element reflectivity difference of the sample 610 is 30% and the element reflectivity difference of the sample 611 is 35%, but the viewing angle dependency is 12 in the sample 610, whereas the sample 611 deteriorates to 27. is doing.
- the difference in element reflectivity of the sample 613 is 29%, and the difference in element reflectivity of the sample 614 is 31%.
- the viewing angle dependency is 12 in the sample 613, but 23 in the sample 614. Yes.
- the difference in element reflectivity of sample 617 is 28%, and the difference in element reflectivity of sample 618 is 31%.
- the viewing angle dependency is 14 in sample 617, but 23 in sample 618. Yes.
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Abstract
Description
なお、説明は以下の順序で行う。
1.有機電界発光素子の第1実施形態
2.有機電界発光素子の第2実施形態
以下、有機電界発光素子の第1実施形態について説明する。
図1に、本実施形態の有機電界発光素子(有機EL素子)の断面模式図を示す。図1に示すように有機EL素子10は、基板11、基板11上に設けられた窒素含有層12、窒素含有層12に接して形成された透明電極13、透明電極13に対向して設けられた反射電極15、及び、透明電極13と反射電極15とに挟持された発光ユニット14を備える。発光ユニット14には、少なくとも1層以上の発光層を有している。これらの基板11、窒素含有層12、透明電極13、発光ユニット14、及び、反射電極15の各構成の詳細は後述する。
素子反射率とは、有機EL素子10の非発光時において、基板11側の正面(0~10°)から入射する光に対する、有機EL素子10の反射率であり、分光光度計や反射率測定器などにより求めることができる。なお、有機EL素子が光散乱構造等を有する場合には、光散乱構造を除いた構成で求められた反射率を、有機EL素子の素子反射率とする。
有機EL素子10の波長450nm~750nmの光における素子反射率の最大値と最小値との差を30%以内とするためには、例えば、以下の構成が求められる。
(1)透明電極13の反射率を低くする。
(2)反射電極15の反射率を高くする。
(3)有機EL素子10の発光ユニット14の厚さを、特定波長に干渉し難い厚さに設計する。
以下に、上述の有機EL素子10の各構成と、波長450nm~750nmの光における素子反射率の最大値と最小値の差との関係を説明する。
まず、透明電極13と素子反射率との関係について説明する。
図2に、透明電極13の反射率と、波長450nm~750nmの光における素子反射率の最大値と最小値の差(素子反射率差)との関係をシミュレートしたグラフを示す。
素子反射率の最大値と最小値は、上述の図1に示す構成の有機EL素子10により求めた。有機EL素子10は、窒素含有層12を75nm、発光ユニット14として有機材料を220nm、反射電極15としてアルミニウムを100nmとした。そして、透明電極13を上述の各所定厚(6~15nm)の銀とした有機EL素子10において、波長450nm~750nmの間で1nm刻みに各波長の素子反射率を求めた。さらに、この各波長の素子反射率の中の最大値と最小値の差(最大反射率%-最小反射率%=素子反射率差%)を求めた。
透明電極13の反射率を低くするためには、透明電極13を薄く形成し、さらに、薄く形成しても光透過特性が低下しない構成とする必要がある。光透過特性には、透明電極13の材料、厚さ、及び、透明電極13の表面形状が影響する。つまり、透明電極13の反射率を低くするためには、薄く形成しても均一性及び平坦性の高い金属層を形成する必要がある。
このため、透明電極13の表面形状は、表面の均一性、平坦性が高いことが好ましい。平坦性が高いことにより、特定波長への干渉を抑制することができる。また、表面の均一性を高めることにより、この特定波長の干渉を抑制することができ、波長依存性を抑制することができる。
次に、反射電極15と素子反射率との関係について説明する。
図4に、反射電極15の反射率と、波長450nm~750nmの光における素子反射率の最大値と最小値の差(素子反射率差)との関係をシミュレートしたグラフを示す。
素子反射率の最大値と最小値は、上述の図1に示す構成の有機EL素子10により求めた。有機EL素子10は、窒素含有層12を75nm、透明電極13として銀を10nm、発光ユニット14として有機材料を220nmとした。そして、反射電極15として上述の各材料を適用した有機EL素子10において、波長450nm~750nmの間で1nm刻みに各波長の素子反射率を求めた。さらに、この各波長の素子反射率の中の最大値と最小値の差(最大反射率%-最小反射率%=素子反射率差%)を求めた。
従って、反射電極15の反射率を高くすることにより、有機EL素子10内での反射電極15による特定波長への影響を抑制し、均一性の高い光を得ることができる。このため、有機EL素子10から取り出される光の波長依存性や、視野角依存性を抑制することができる。
反射電極15の反射率を高めるためには、反射率の高い材料を用いる。例えば、上述のシミュレーションにおいて90%以上の反射率を示す銀やアルミニウム等を用いることが好ましい。
銀を陰極として用いる場合には、電子注入性を高めるために、例えば、銀と発光ユニット14との間にアルミニウムを1nm程度形成し、陰極を銀とアルミニウムとの積層構造とすることも可能である。この構成では、アルミニウムを挟むことにより、反射電極15の反射率の低下が懸念されるものの、アルミニウムの厚さが1nm程度と非常に薄いため、光学的な影響を小さく抑えて、電子注入性を高めることが可能となる。
また、発光ユニット14の構成で電子注入性を向上させることにより、銀を直接発光ユニット14に接する構成とすることも可能である。例えば、銀と接する層に、有機材料と無機塩/錯体の混合物を用いることで、発光ユニット14への電子注入性が改善できる。このため、反射率を低下させずに、銀による反射電極15を形成することができる。
反射電極15の表面形状は、表面の均一性、平坦性が高いことが好ましい。平坦性が高いことにより、波長の干渉が小さい構成となる。例えば、特定周期の凹凸が表面に存在する場合には、反射電極15で光反射する際に、凹凸の周期に干渉を受けて特定の波長が強められたり、弱められたりする。このため、特定の波長依存が発生してしまう。表面の平坦性を高めることにより、この特定波長への干渉を抑制することができるため、波長依存性を抑制することができる。
次に、発光ユニット14の厚さと素子反射率との関係について説明する。
図6に、発光ユニット14の厚さと、波長450nm~750nmの光における素子反射率の最大値と最小値の差(素子反射率差)との関係をシミュレートしたグラフを示す。
素子反射率の最大値と最小値は、上述の図1に示す構成の有機EL素子10により求めた。有機EL素子10は、窒素含有層12を75nm、透明電極13として銀を10nm、反射電極15としてアルミニウムを100nmとした。そして、発光ユニット14として、厚さを80nm~400nmの間で変更した有機EL素子10において、波長450nm~750nmの間で1nm刻みに各波長の素子反射率を求めた。さらに、この各波長の素子反射率の中の最大値と最小値の差(最大反射率%-最小反射率%=素子反射率差%)を求めた。
また、各波長での素子反射率は、発光ユニット14の厚さに対して、例えば、ある厚さでは短波長側で反射率が低下し、違う厚さでは中間波長域で反射率が低下したり、短波長側で素子反射率が高く長波長側にかけて緩やかに反射率が低下したり、短波長側や長波長側で反射率が高く中間波長域において素子反射率が低下する等の様々な挙動を見せる。
このように、波長により干渉を受けやすい厚さが異なるため、発光ユニット14の厚さに応じた素子反射率の波長依存が発生する。
有機EL素子10において、波長450nm~750nmの光における素子反射率の最大値と最小値との差を30%以内とするためには、素子反射率の最大値と最小値との差が30%以内となる厚さで発光ユニット14を設計する必要がある。つまり、有機EL素子10の発光ユニット14の厚さが、特定波長に干渉し難い厚さに設計されていることが好ましい。
発光ユニット14の厚さを変えた場合には、波長450nm~750nmの光における素子反射率の最大値と最小値との差(素子反射率差)を表すグラフが、上述のように複雑な挙動を見せる傾向がある。一方、発光ユニット14の厚さを一定にし、透明電極13や反射電極15を変更した場合には、波長450nm~750nmの光における素子反射率差を表すグラフは、周期的な安定した挙動となる傾向がある。
図6に示すグラフから、発光ユニット14の厚さが220nmのときには、波長450nm~750nmの光における素子反射率差が30%以内となっているもののわずかに30%を下回る約29%である。このため、発光ユニット14の厚さを220nmとした場合には、波長450nm~750nmの光における素子反射率差を30%以内とするためには、透明電極13の反射率や反射電極15の反射率に対する余裕が無く、これらの構成の設計自由度が低くなる。従って、透明電極13の厚さを大きくして透明電極13の反射率を高くする構成や、反射電極15の材料をアルミニウムよりも反射率の低い材料に変更することが難しい。
つまり、有機EL素子10の設計自由度が向上する。
同様に、銀等を用いて反射電極15の反射率を上げることにより、透明電極13の厚さを大きくして反射率が上がったとしても、波長450nm~750nmの光における素子反射率差が30%以内となる構成を、実現することが可能になる。
(発光ユニットの中間層)
発光ユニット14が、複数の発光層を有する、いわゆるタンデム構造やスタック構造等である場合には、透明電極13と反射電極15との間に形成される発光ユニットの合計の厚さが、上述のように、特定波長に干渉し難い厚さに設計されていることが好ましい。
また、上記構造において、発光ユニット間に設けられる中間層は、上述の透明電極13と同様に、反射率が低く、光透過特性に優れた層とすることが好ましい。反射率が低く透過性が高いことにより、中間層と反射電極15、及び、中間層と透明電極13との多重反射を抑制し、有機EL素子10から取り出される光の波長依存性や、視野角依存性を抑制することができる。
中間層としては、例えば、アルミニウム、カルシウム、リチウム等を用いて、1nm程度とすることにより、反射率の低減及び光透過特性の向上が可能となる。特に、カルシウム、リチウム等を用いることにより、反射率の低減及び光透過特性の向上が可能となる。
有機EL素子10において、発光ユニット14は主に有機材料から形成されるが、この発光ユニット14は光吸収が少なく、特定波長に干渉しにくい材料により構成されることが好ましい。
特定波長に吸収を有する材料や、有色の材料等を用いると、有機EL素子10の波長依存性が高くなる。このため、発光ユニット14自体は、光の減衰や吸収が小さいことが好ましい。
特に、タンデム構造のように、発光ユニット14の厚さが大きくなりやすい構成の場合には、発光ユニット14内での減衰や吸収が特に少ないことが好ましく、特定波長において減衰や吸収がほとんどないことがさらに好ましい。
光散乱層を導入することにより、光取り出し効率を上げ、視野角依存性を低減することができる。
この場合、特に、波長450nm~750nmの光における素子反射率差を30%以内とした有機EL素子に光散乱層を形成すると、30%を超える有機EL素子と比較し、効率向上幅が大きくなり、また、視野角依存性の低下幅も大きくなる。
また、光散乱層以外にも、有機EL素子の光取り出し側に、光取り出し効率を上げるための光学部材が設けられていてもよい。この場合にも、波長450nm~750nmの光における素子反射率差を30%以内とした有機EL素子に光学部材を形成すると、30%を超える有機EL素子と比較し、効率向上幅が大きくなり、また、視野角依存性の低下幅も大きくなる。
なお、光散乱層や光学部材等を導入すると見た目が変化するため、アプリケーションに応じて適宜選択が必要となる。
上述の図1に示す有機EL素子10を構成する、基板11、窒素含有層12、透明電極13、発光ユニット14、及び、反射電極15の詳細について説明する。
有機EL素子10に用いることができる基板11としては、ガラス、プラスチック等の種類には特に限定はなく、また透明であっても不透明であってもよい。基板11側から光を取り出す場合には、基板11は透明であることが好ましい。好ましく用いられる透明な基板11としては、ガラス、石英、透明樹脂フィルムを挙げることができる。特に好ましい基板11は、有機EL素子10にフレキシブル性を与えることが可能な樹脂フィルムである。
窒素含有層12は、透明電極13に隣接して形成され、基板11と透明電極13とに挟持された層である。
窒素含有層12と接して透明電極13が形成されることにより、透明電極13の主成分である銀と、窒素含有層12を構成する窒素原子を含んだ化合物との相互作用により、窒素含有層表面における銀原子の拡散距離が減少し、銀の凝集が抑えられる。このため、一般的に、核成長型(Volumer-Weber:VW型)での成長により島状に孤立し易い薄銀層が、単層成長型(Frank-van der Merwe:FM型)の成長によって形成される。従って、窒素含有層12に接して、銀を主成分とする透明電極13を形成することにより、薄いながらも、均一な厚さの透明電極13が得られる。
窒素原子は、第15族元素であり、最外殻に5個の電子を有する。このうち3個の不対電子は他の原子との共有結合に用いられ、残りの2個は一対の非共有電子対となる。このため、通常、窒素原子の結合本数は3本である。
例えば、窒素原子を有する基として、アミノ基(-NR1R2)、アミド基(-C(=O)NR1R2)、ニトロ基(-NO2)、シアノ基(-CN)、ジアゾ基(-N2)、アジド基(-N3)、ウレア結合(-NR1C=ONR2-)、イソチオシアネート基(-N=C=S)、チオアミド基(-C(=S)NR1R2)などが挙げられる。尚、R1,R2は、それぞれ水素原子(H)又は置換基である。これらの基を構成する窒素原子の非共有電子対は、芳香族性に関与せずかつ金属に配位していないため、[有効非共有電子対]に該当する。このうち、ニトロ基(-NO2)の窒素原子が有する非共有電子対は、酸素原子との共鳴構造に利用されているものの、以降の実施例で示すように良好な効果が得られていることから、芳香族性に関与せずかつ金属に配位していない[有効非共有電子対]として窒素上に存在すると考えられる。
以下に、窒素含有層12を構成する化合物として、上述した有効非共有電子対含有率[n/M]が2.0×10-3≦[n/M]を満たす化合物の具体例(No.1~No.48)を示す。各化合物No.1~No.48には、[有効非共有電子対]を有する窒素原子に対して○を付した。また、下記表1には、これらの化合物No.1~No.48の分子量M、[有効非共有電子対]の数n、及び有効非共有電子対含有率[n/M]を示す。下記化合物33の銅フタロシアニンにおいては、窒素原子が有する非共有電子対のうち銅に配位していない非共有電子対が[有効非共有電子対]としてカウントされる。
また、窒素含有層12を構成する化合物としては、以上のような有効非共有電子対含有率[n/M]が上述した所定範囲である化合物に加え、他の化合物を用いてもよい。窒素含有層12に用いられる他の化合物は、有効非共有電子対含有率[n/M]が上述した所定範囲で有る無しにかかわらず、窒素原子を含有する化合物が好ましく用いられる。中でも[有効非共有電子対]を有する窒素原子を含有する化合物が特に好ましく用いられる。また窒素含有層12に用いられる他の化合物は、この窒素含有層12を備える有機EL素子10ごとに必要とされる性質を有する化合物が用いられる。窒素含有層12が、有機EL素子10に用いられる場合、その成膜性や、電子輸送性の観点から、窒素含有層12を構成する化合物として、以降に説明する一般式(1)~(8a)で表される構造を有する化合物が好ましく用いられる。
また窒素含有層12を構成するさらに他の化合物として、以上のような一般式(1)~(8a)で表される構造を有する化合物の他、下記に具体例を示す化合物1~166が例示される。これらの化合物は、透明電極13を構成する銀と相互作用する窒素原子を含有する化合物である。また、これらの化合物は、電子輸送性又は電子注入性を備えた材料である。従って、これらの化合物を用いて構成した窒素含有層12は、有機EL素子10として好適であり、有機EL素子10における電子輸送層又は電子注入層として窒素含有層12を用いることができる。尚、これらの化合物1~166の中には、上述した有効非共有電子対含有率[n/M]の範囲に当てはまる化合物も含まれ、このような化合物であれば単独で窒素含有層12を構成する化合物として用いることができる。さらに、これらの化合物1~166の中には、上述した一般式(1)~(8a)に当てはまる化合物もある。
以下に代表的な化合物の合成例として、化合物5の具体的な合成例を示すが、これに限定されない。
窒素雰囲気下において、2,8-ジブロモジベンゾフラン(1.0モル)、カルバゾール(2.0モル)、銅粉末(3.0モル)、炭酸カリウム(1.5モル)を、DMAc(ジメチルアセトアミド)300ml中で混合し、130℃で24時間撹拌した。これによって得た反応液を室温まで冷却後、トルエン1Lを加え、蒸留水で3回洗浄し、減圧雰囲気下において洗浄物から溶媒を留去した。残渣をシリカゲルフラッシュクロマトグラフィー(n-ヘプタン:トルエン=4:1~3:1)にて精製し、中間体1を収率85%で得た。
室温、大気下で中間体1(0.5モル)をDMF(ジメチルホルムアミド)100mlに溶解し、NBS(N-ブロモコハク酸イミド)(2.0モル)を加え、一晩室温で撹拌した。得られた沈殿物を濾過し、メタノールで洗浄し、中間体2を収率92%で得た。
窒素雰囲気下において、中間体2(0.25モル)、2-フェニルピリジン(1.0モル)、ルテニウム錯体[(η6-C6H6)RuCl2]2(0.05モル)、トリフェニルホスフィン(0.2モル)、炭酸カリウム(12モル)を、NMP(N-メチル-2-ピロリドン)3L中で混合し、140℃で一晩撹拌した。
以上のような窒素含有層12が基板11上に形成されたものである場合、その形成方法としては、塗布法、インクジェット法、コーティング法、ディップ法等のウェットプロセスを用いる方法や、蒸着法(抵抗加熱、EB法等)、スパッタ法、CVD法等のドライプロセスを用いる方法等が挙げられる。なかでも蒸着法が好ましく適用される。
透明電極13は、上述のように、有機EL素子10の450nm~750nmの素子反射率の最大値と最小値との差が30%以内となるように薄く形成し、さらに、薄く形成しても光透過特性が低下しない構成とする必要がある。
透明電極13を構成する銀(Ag)を主成分とする合金は、一例として銀マグネシウム(AgMg)、銀銅(AgCu)、銀パラジウム(AgPd)、銀パラジウム銅(AgPdCu)、銀インジウム(AgIn)等が挙げられる。
また、この透明電極13は、厚さが4~15nmの範囲にあることが好ましい。厚さ15nm以下では、層の吸収成分及び反射成分が低く抑えられ、透明電極13の光透過率が維持されるため好ましい。また、厚さが4nm以上であることにより、層の導電性も確保される。
従って、窒素含有層12に接して、銀を主成分とする金属層を形成することにより、薄く形成しても均一な透明電極13が得られる。
従って、有機EL素子10の波長依存性を抑制することができ、450nm~750nmの素子反射率の最大値と最小値との差を減少させることができる。
発光ユニット14は、陽極と陰極との間に設けられ、発光性を有する有機材料層を含む発光層を少なくとも一層以上備える。また、発光ユニット14は、発光層と電極との間に他の層を備えていてもよい。
発光ユニット14は、上述のように有機EL素子10の450nm~750nmの素子反射率の最大値と最小値との差が30%以内となるように、厚さを調整する必要がある。このため、有機EL素子10の450nm~750nmの素子反射率の最大値と最小値との差が30%以内となるように、発光ユニット14の総厚を設定し、この総厚となるように発光ユニット14を構成する各層の厚さをそれぞれ調整する必要がある。さらに、設定した発光ユニット14の総厚を満たすとともに、発光ユニット14を構成する各層で要求される機能の弊害とならないように、各層の厚さを調整する。
(1)陽極/発光層/陰極
(2)陽極/発光層/電子輸送層/陰極
(3)陽極/正孔輸送層/発光層/陰極
(4)陽極/正孔輸送層/発光層/電子輸送層/陰極
(5)陽極/正孔輸送層/発光層/電子輸送層/電子注入層/陰極
(6)陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/陰極
(7)陽極/正孔注入層/正孔輸送層/(電子阻止層/)発光層/(正孔阻止層/)電子輸送層/電子注入層/陰極
上記の中で(7)の構成が好ましく用いられるが、これに限定されるものではない。
上記の代表的な素子構成において、陽極と陰極を除く層が、発光性を有する発光ユニット14である。
また、必要に応じて、発光層と陰極との間に正孔阻止層(正孔障壁層)や電子注入層(陰極バッファー層)等を設けてもよく、また、発光層と陽極との間に電子阻止層(電子障壁層)や正孔注入層(陽極バッファー層)等を設けてもよい。
電子輸送層は、電子を輸送する機能を有する層である。電子輸送層には、広い意味で電子注入層、及び、正孔阻止層も含まれる。また、電子輸送層は、複数層で構成されていてもよい。
正孔輸送層は、正孔を輸送する機能を有する層である。正孔輸送層には、広い意味で正孔注入層、及び、電子阻止層も含まれる。また、正孔輸送層は、複数層で構成されていてもよい。
以下、発光ユニット14を構成する各層について説明する。
発光ユニット14に用いる発光層は、電極又は隣接層から注入される電子と正孔とが再結合し、励起子を経由して発光する場を提供する。発光層において、発光する部分は発光層の層内であっても、発光層と隣接層との界面であってもよい。
発光層に用いられる発光ドーパントとしては、蛍光発光性ドーパント(蛍光ドーパント、蛍光性化合物ともいう)、及び、リン光発光性ドーパント(リン光ドーパント、リン光性化合物ともいう)が好ましく用いられる。これらのうち、少なくとも1層の発光層がリン光発光ドーパントを含有することが好ましい。
有機EL素子10における白色としては、2度視野角正面輝度を前述の方法により測定した際に、1000cd/m2でのCIE1931表色系における色度がx=0.39±0.09、y=0.38±0.08の領域内にあることが好ましい。
リン光発光性ドーパントは、励起三重項からの発光が観測される化合物であり、具体的には、室温(25℃)にてリン光発光する化合物であり、25℃においてリン光量子収率が0.01以上の化合物である。発光層に用いるリン光発光性ドーパントにおいて、好ましいリン光量子収率は0.1以上である。
一つは、キャリアが輸送されるホスト化合物上で、キャリアの再結合によるホスト化合物の励起状態が生成される。このエネルギーをリン光発光性ドーパントに移動させることでリン光発光性ドーパントからの発光を得るというエネルギー移動型である。もう一つは、リン光発光性ドーパントがキャリアトラップとなり、リン光発光性ドーパント上でキャリアの再結合が起こり、リン光発光性ドーパントからの発光が得られるというキャリアトラップ型である。いずれの場合においても、リン光発光性ドーパントの励起状態のエネルギーは、ホスト化合物の励起状態のエネルギーよりも低いことが条件となる。
公知のリン光発光性ドーパントの具体例としては、以下の文献に記載されている化合物等が挙げられる。
蛍光発光性ドーパントは、励起一重項からの発光が可能な化合物であり、励起一重項からの発光が観測される限り特に限定されない。
遅延蛍光を利用した発光ドーパントの具体例としては、例えば、国際公開第2011/156793号、特開2011-213643号、特開2010-93181号等に記載の化合物が挙げられる。
ホスト化合物は、発光層において主に電荷の注入および輸送を担う化合物であり、有機EL素子においてそれ自体の発光は実質的に観測されない。
好ましくは室温(25℃)においてリン光発光のリン光量子収率が、0.1未満の化合物であり、さらに好ましくは、リン光量子収率が0.01未満の化合物である。また、発光層に含有される化合物の内で、その層中での質量比が20%以上であることが好ましい。
ホスト化合物は、単独で用いてもよく、または複数種を併用して用いてもよい。ホスト化合物を複数種用いることで、電荷の移動を調整することが可能であり、有機EL素子10の高効率化が可能となる。
ここで、ガラス転移点(Tg)とは、DSC(Differential Scanning Calorimetry:示差走査熱量法)を用いて、JIS-K-7121に準拠した方法により求められる値である。
特開2001-257076号公報、同2002-308855号公報、同2001-313179号公報、同2002-319491号公報、同2001-357977号公報、同2002-334786号公報、同2002-8860号公報、同2002-334787号公報、同2002-15871号公報、同2002-334788号公報、同2002-43056号公報、同2002-334789号公報、同2002-75645号公報、同2002-338579号公報、同2002-105445号公報、同2002-343568号公報、同2002-141173号公報、同2002-352957号公報、同2002-203683号公報、同2002-363227号公報、同2002-231453号公報、同2003-3165号公報、同2002-234888号公報、同2003-27048号公報、同2002-255934号公報、同2002-260861号公報、同2002-280183号公報、同2002-299060号公報、同2002-302516号公報、同2002-305083号公報、同2002-305084号公報、同2002-308837号公報、米国特許公開第20030175553号、米国特許公開第20060280965号、米国特許公開第20050112407号、米国特許公開第20090017330号、米国特許公開第20090030202号、米国特許公開第20050238919号、国際公開第2001039234号、国際公開第2009021126号、国際公開第2008056746号、国際公開第2004093207号、国際公開第2005089025号、国際公開第2007063796号、国際公開第2007063754号、国際公開第2004107822号、国際公開第2005030900号、国際公開第2006114966号、国際公開第2009086028号、国際公開第2009003898号、国際公開第2012023947号、特開2008-074939号公報、特開2007-254297号公報、EP2034538等である。
有機EL素子10に用いる電子輸送層とは、電子を輸送する機能を有する材料からなり、陰極より注入された電子を発光層に伝達する機能を有する。
電子輸送材料は単独で用いてもよく、また複数種を併用して用いてもよい。
電子輸送層の総厚については特に制限はないが、通常は2nm~5μmの範囲であり、より好ましくは2nm~500nmであり、さらに好ましくは5nm~200nmである。
従って、有機EL素子10では、450nm~750nmの素子反射率の最大値と最小値との差が30%以内となるように、発光ユニット14の総厚を設定する。この発光ユニット14の総厚の調整は、電子輸送層の総膜厚を数nm~数μmの間で適宜調整することで行なうことが好ましい。
一方で、電子輸送層の膜厚を厚くすると電圧が上昇しやすくなるため、特に膜厚が厚い場合においては、電子輸送層の電子移動度は10-5cm2/Vs以上であることが好ましい。
芳香族炭化水素環誘導体としては、ナフタレン誘導体、アントラセン誘導体、トリフェニレン等が挙げられる。
また、これらの材料を高分子鎖に導入した、またはこれらの材料を高分子の主鎖とした高分子材料を用いることもできる。
米国特許第6528187号 、米国特許第7230107号、米国特許公開第20050025993号 、米国特許公開第20040036077号 、米国特許公開第20090115316号 、米国特許公開第20090101870号 、米国特許公開第20090179554号 、国際公開第2003060956号、国際公開第2008132085号、Appl. Phys. Lett. 75, 4 (1999)、Appl. Phys. Lett. 79, 449 (2001)、Appl. Phys. Lett. 81, 162 (2002)、Appl. Phys. Lett. 81, 162 (2002)、Appl. Phys. Lett. 79, 156 (2001)、米国特許第7964293号、米国特許公開第2009030202号、国際公開第2004080975号、国際公開第2004063159号、国際公開第2005085387号、国際公開第2006067931号、国際公開第2007086552号、国際公開第2008114690号、国際公開第2009069442号、国際公開第2009066779号、国際公開第2009054253号、国際公開第2011086935号、国際公開第2010150593号、国際公開第2010047707号、EP2311826号、特開2010-251675号公報、特開2009-209133号公報、特開2009-124114号公報、特開2008-277810号公報、特開2006-156445号公報、特開2005-340122号公報、特開2003-45662号公報、特開2003-31367号公報、特開2003-282270号公報、国際公開第2012115034号等
正孔阻止層は、広い意味では電子輸送層の機能を有する層である。好ましくは、電子を輸送する機能を有しつつ、正孔を輸送する能力が小さい材料からなる。電子を輸送しつつ正孔を阻止することで、電子と正孔の再結合確率を向上させることができる。
また、上述の電子輸送層の構成を、必要に応じて正孔阻止層として用いることができる。
有機EL素子10に設ける正孔阻止層は、発光層の陰極側に隣接して設けられることが好ましい。
正孔阻止層に用いられる材料としては、上述の電子輸送層に用いられる材料が好ましく用いられ、また、上述のホスト化合物として用いられる材料も正孔阻止層に好ましく用いられる。
電子注入層(「陰極バッファー層」ともいう)は、駆動電圧低下や発光輝度向上のために陰極と発光層との間に設けられる層である。電子注入層の一例は、「有機EL素子とその工業化最前線(1998年11月30日エヌ・ティー・エス社発行)」の第2編第2章「電極材料」(123~166頁)に記載されている。
電子注入層はごく薄い膜であることが好ましく、素材にもよるがその膜厚は0.1nm~5nmの範囲が好ましい。また構成材料が断続的に存在する不均一な膜であってもよい。
また、上記の電子注入層に用いられる材料は単独で用いてもよく、複数種を併用して用いてもよい。
正孔輸送層は、正孔を輸送する機能を有する材料からなる。正孔輸送層は、陽極より注入された正孔を発光層に伝達する機能を有する層である。
有機EL素子10において、正孔輸送層の総膜厚に特に制限はないが、通常は5nm~5μmの範囲であり、より好ましくは2nm~500nmであり、さらに好ましくは5nm~200nmである。
また、特表2003-519432号公報や特開2006-135145号公報等に記載されているヘキサアザトリフェニレン誘導体も正孔輸送材料として用いることができる。
また、特開平11-251067号公報、J.Huang et.al.著文献(Applied Physics Letters 80(2002),p.139)に記載されているような、所謂p型正孔輸送材料やp型-Si、p型-SiC等の無機化合物を用いることもできる。さらにIr(ppy)3に代表されるような中心金属にIrやPtを有するオルトメタル化有機金属錯体も好ましく用いられる。
正孔輸送材料の具体例としては、上記で挙げた文献の他、以下の文献に記載の化合物等が挙げられるが、これらに限定されない。
Appl. Phys. Lett. 69, 2160 (1996)、J. Lumin. 72-74, 985 (1997)、Appl. Phys. Lett. 78, 673 (2001)、Appl. Phys. Lett. 90, 183503 (2007)、Appl. Phys. Lett. 90, 183503 (2007)、Appl. Phys. Lett. 51, 913 (1987)、Synth. Met. 87, 171 (1997)、Synth. Met. 91, 209 (1997)、Synth. Met. 111,421 (2000)、SID Symposium Digest, 37, 923 (2006)、J. Mater. Chem. 3, 319 (1993)、Adv. Mater. 6, 677 (1994)、Chem. Mater.15,3148 (2003)、米国特許公開第20030162053号、米国特許公開第20020158242号、米国特許公開第20060240279号、米国特許公開第20080220265号、米国特許第5061569号、国際公開第2007002683号、国際公開第2009018009号、EP650955、米国特許公開第20080124572号、米国特許公開第20070278938号、米国特許公開第20080106190号、米国特許公開第20080018221号、国際公開第2012115034号、特表2003-519432号公報、特開2006-135145号、米国特許出願番号13/585981号
電子阻止層は、広い意味では正孔輸送層の機能を有する層である。好ましくは、正孔を輸送する機能を有しつつ電子を輸送する能力が小さい材料からなる。電子阻止層は、正孔を輸送しつつ電子を阻止することで、電子と正孔の再結合確率を向上させることができる。
また、上述の正孔輸送層の構成を必要に応じて、有機EL素子10の電子阻止層として用いることができる。有機EL素子10に設ける電子阻止層は、発光層の陽極側に隣接して設けられることが好ましい。
電子阻止層に用いられる材料としては、上述の正孔輸送層に用いられる材料が好ましく用いることができる。また、上述のホスト化合物として用いられる材料も、電子阻止層として好ましく用いることができる。
正孔注入層(「陽極バッファー層」ともいう)は、駆動電圧低下や発光輝度向上のために陽極と発光層との間に設けられる層である。正孔注入層の一例は、「有機EL素子とその工業化最前線(1998年11月30日エヌ・ティー・エス社発行)」の第2編第2章「電極材料」(123~166頁)に記載されている。
正孔注入層は必要に応じて設けられ、上述のように陽極と発光層との間、又は、陽極と正孔輸送層との間に設けられる。
正孔注入層に用いられる材料は、例えば上述の正孔輸送層に用いられる材料等が挙げられる。中でも、銅フタロシアニンに代表されるフタロシアニン誘導体、特表2003-519432号公報や特開2006-135145号公報等に記載されているようなヘキサアザトリフェニレン誘導体、酸化バナジウムに代表される金属酸化物、アモルファスカーボン、ポリアニリン(エメラルディン)やポリチオフェン等の導電性高分子、トリス(2-フェニルピリジン)イリジウム錯体等に代表されるオルトメタル化錯体、トリアリールアミン誘導体等が好ましい。
上述の正孔注入層に用いられる材料は単独で用いてもよく、また複数種を併用して用いてもよい。
有機EL素子10を構成する発光ユニット14は、更に他の含有物を含んでもよい。
含有物としては、例えば臭素、ヨウ素及び塩素等のハロゲン元素やハロゲン化化合物、Pd、Ca、Na等のアルカリ金属やアルカリ土類金属、遷移金属の化合物や錯体、塩等が挙げられる。
含有物の含有量は、任意に決定することができるが、含有される層の全質量%に対して1000ppm以下であることが好ましく、より好ましくは500ppm以下であり、さらに好ましくは50ppm以下である。
ただし、電子や正孔の輸送性を向上させる目的や、励起子のエネルギー移動を有利にするための目的などによってはこの範囲内ではない。
有機EL素子10の発光ユニット14(正孔注入層、正孔輸送層、発光層、正孔阻止層、電子輸送層、電子注入層等)の形成方法について説明する。
発光ユニット14の形成方法は、特に制限はなく、従来公知の例えば真空蒸着法、湿式法(ウェットプロセス)等により形成することができる。
反射電極15は、上述のように、有機EL素子10の450nm~750nmの素子反射率の最大値と最小値との差が30%以内となるように、反射率の高い材料を用いる必要がある。さらに、反射光の特定の波長に干渉しないように、表面の均一性、平坦性が高いことが必要となる。
(光散乱層)
光散乱層は、波長550nmにおける屈折率が1.7以上2.5未満の範囲内である高屈折率層であることが好ましい。有機発光素子の発光層内に閉じ込められる導波モード光や反射電極から反射されるプラズモンモード光は特異な光学モードの光であり、これらの光を取り出すためには少なくとも1.7以上の屈折率が必要である。一方、プラズモンモードの最も高次側のモードであっても屈折率2.5以上の領域の光は略存在せず、これ以上の屈折率としても取り出せる光の量が増えることはない。
また、光散乱層は、樹脂と粒子との混合物による屈折率差を利用した混合散乱層(散乱膜)としてもよいし、凹凸構造等の形状制御により形成された形状制御散乱層としてもよい。
光散乱層は、光取り出し効率を向上させる層であり、透過率50%以上であることが好ましく、55%以上であることがより好ましく、60%以上であることが特に好ましい。
次に、有機電界発光素子の第2実施形態について説明する。
図12に、本実施形態の有機電界発光素子(有機EL素子)の断面模式図を示す。図12に示すように有機EL素子20は、発光ユニットが積層された、いわゆるタンデム構造である。
有機EL素子20は、基板21、基板21上に設けられた窒素含有層22、窒素含有層22に接して形成された透明電極23、透明電極23上に設けられた第1発光ユニット24、第1発光ユニット24上に設けられた中間層25、中間層25を介して第1発光ユニット24上に設けられた第2発光ユニット26、及び、第2発光ユニット26上に設けられた反射電極27を備える。
また、有機EL素子20においては、透明電極23から反射電極27までの間に形成される第1発光ユニット24、中間層25、及び、第2発光ユニット26の合計の厚さが、上述の第1実施形態の有機EL素子における発光ユニットの厚さに該当する。
従って、有機EL素子20において、透明電極23、反射電極27、並びに、第1発光ユニット24、中間層25、及び、第2発光ユニット26の合計の厚さを、波長450nm~750nmの光における素子反射率の最大値と最小値との差を30%以内に減少させるために、第1実施形態と同様の最適化を図る必要がある。これらの構成の最適化の方法は、上述の第1実施形態と同様であるため、説明を省略する。
タンデム構造の代表的な素子構成としては、例えば以下の構成を挙げることができる。
(1)陽極/第1発光ユニット/中間層/第2発光ユニット/陰極
(2)陽極/第1発光ユニット/中間層/第2発光ユニット/中間層/第3発光ユニット/陰極
ここで、上記第1発光ユニット、第2発光ユニット及び第3発光ユニットは全て同じであっても、異なっていてもよい。また、2つの発光ユニットが同じであり、残る1つが異なっていてもよい。各発光ユニットは、上述の第1実施形態と同様の構成とすることができる。
タンデム構造の有機EL素子20では、中間層25が透明電極23と同様に、反射率が低く、光透過特性に優れた層とすることが好ましい。反射率が低く透過性が高いことにより、中間層25と反射電極27、及び、中間層25と透明電極23との多重反射を抑制し、有機EL素子20から取り出される光の波長依存性や、視野角依存性を抑制することができる。
次に、第2実施形態の有機電界発光素子の変形例について説明する。
図13に、変形例の有機電界発光素子(有機EL素子)の断面模式図を示す。図13に示すように有機EL素子20Aは、上述の第2実施形態の有機EL素子のタンデム構造から、中間層が省略された構成である。有機EL素子20Aは中間層を有していないことを除き、上述の図12に示す第2実施形態の有機EL素子20と同様の構成である。このため、有機EL素子20Aを構成する各層についての説明は省略する。
タンデム構造において中間層を設けない場合には、中間層による反射を考慮する必要がないため、第1発光ユニット24と第2発光ユニット26は合計の厚さは、波長450nm~750nmの光における素子反射率差が30%以内となるように最適化されていればよく、それぞれの層の厚さは特に限定されない。
例えば、第1発光ユニット24の最上層にn型の電子輸送層を形成し、第2発光ユニット26の最下層にp型の正孔輸送層を形成することで、第1発光ユニット24と第2発光ユニット26との界面において電荷の発生が可能な構成となる。
p型の正孔輸送層としては、例えば、p型の不純物をゲスト材料としてドープして、p性の高い(正孔リッチ)正孔輸送層を用いることもできる。また、p型正孔輸送材料やp型-Si、p型-SiC等の無機化合物を用いることもできる。
試料101~112の各有機EL素子を、以下に示す手順で作製して評価した。
(基板)
まず、50mm×50mm、厚さ0.7mmのガラス製の透明支持基板上をイソプロピルアルコールで超音波洗浄し、乾燥窒素ガスで乾燥し、UVオゾン洗浄を5分間行った。
次に、上記透明支持基板を市販の真空蒸着装置の基板ホルダーに固定した。そして、真空蒸着装置内の蒸着用るつぼの各々に、有機EL素子の各層の構成材料を、各々素子作製に最適の量で充填した。蒸着用るつぼはモリブデン製またはタングステン製の抵抗加熱用材料で作製されたものを用いた。
次に、形成した下地層上に銀を0.3nm/秒で8nm蒸着し、陽極を形成した。
次に、形成した陽極上に、化合物M-2の入った蒸着用るつぼに通電して加熱し、蒸着速度0.1nm/秒で透明支持基板に蒸着し、膜厚120nmの正孔注入輸送層を形成した。
さらに、化合物GD-1,RD-1及び化合物H-2を、化合物GD-1が17%、RD-1が0.8%の濃度になるように蒸着速度0.1nm/秒で共蒸着し、膜厚15nmの黄色を呈するリン光発光層を形成した。
その後、化合物E-1を蒸着速度0.1nm/秒、フッ化カリウム(KF)を蒸着速度0.01nm/秒で共蒸着し、膜厚80nmの電子輸送層を形成した。
次に、形成した発光ユニットの電子輸送層上に、アルミニウムを蒸着して膜厚100nmの陰極を形成した。
最後に、陰極まで形成した有機EL素子の非発光面をガラスケースで覆い、試料101の有機EL素子を作製した。なお、有機EL素子の発光サイズは20×20mmとした。
陽極を表2に示す厚さ(8nm,10nm,12nm)に変更し、さらに、陰極を表2に示す材料(Al,Ag,Ca)に変更し、上述の試料101と同様の手法を用いて、試料102~109の有機EL素子を作製した。
陽極を表2に示す厚さ(8nm,10nm,12nm)に変更し、さらに、陰極として蒸着法を用いてアルミニウムを1nm製膜した後、銀を100nm製膜して試料110~112の有機EL素子を作製した。これ以外は、上述の試料101と同様の手法を用いて、試料110~112の有機EL素子を作製した。
(素子反射率差)
素子反射率の反射率の差は、上述の図1に示す方法により波長450nm~750nmの各波長の素子反射率を求め、この各波長の素子反射率の中の最大値と最小値の差(最大反射率%-最小反射率%=素子反射率差%)を求めた。
ADC製直流電圧/電流発生器6243を用いて、素子に30A/m2の電流を流しコニカミノルタ製CS-2000を用いて素子効率を測定した。
視野角依存性は正面の色と、最も異なる角度の色の差として、以下のように求めた。
素子を0度~80度の間で、5度おきに、素子を回転しながら各角度で輝度、色度を測定した。そのとき、CIEx、CIEyから、各角度における正面色度からのずれを求めた。各角度のΔExyのうち一番大きい値を視野角依存の値とした。
ΔExy=[(x(各角度)-x(0度))2+(y(各角度)-y(0度))](1/2)
表2に示す結果から、素子反射率差が30%以下の試料では、素子効率が高く、さらに、視野角依存性が小さい結果が得られた。これに対し、素子反射率差が30%を超える試料では、素子効率が低下し、視野角依存性が増加する結果が得られた。
従って、この結果から、波長450nm~750nmの光における素子反射率の最大値と最小値との差を30%以下とすることにより、素子効率、及び、視野角依存性に優れた有機EL素子を実現することができる。
さらに、陰極をCaにより構成した試料では、陰極をAl、Agにより形成した試料よりも素子反射率差が大きくなった。この結果から、陰極の反射率が素子反射率差に影響を与えること、陰極の反射率が高いほど素子反射率差が低くなることがわかる。
試料201~212の各有機EL素子を作製して評価した。
試料201~212の各有機EL素子は、表3に示すように、正孔注入輸送層の膜厚を調整して発光ユニットの厚さを変更し、上述の実施例1の試料102又は試料105と同様の手法を用いて作製した。
そして、上述の実施例1と同様の方法で素子反射率差、素子効率、及び、視野角依存性を測定した。なお、量子効率と視野角依存性は、試料101からの相対値として求めた。
試料201~212の構成、並びに、素子反射率差、素子効率、及び、視野角依存性の測定結果を下記表3に示す。
表3に示す結果から、素子反射率差が30%以下の試料では、素子効率が高く、さらに、視野角依存性が小さい結果が得られた。これに対し、素子反射率差が30%を超える試料では、素子効率が低下し、視野角依存性が増加する結果が得られた。
従って、表3に示す結果から、発光ユニットの厚さにより各波長の素子反射率に影響を与えることがわかる。
さらに、発光ユニットの厚さが各波長の素子反射率差に影響を与えた場合にも、波長450nm~750nmの光における素子反射率の最大値と最小値との差を30%以下とすることにより、素子効率、及び、視野角依存性に優れた有機EL素子を実現することができる。
試料301~322の各有機EL素子を作製して評価した。
試料301~322は、基板上に下記の光散乱層を形成し、この光散乱層上に陽極を形成した以外は、上述の実施例1の試料101~112、及び、実施例2の201,203~207,209~212と同様の手法を用いて作製した。
表4に、試料301~322の有機EL素子の構成に対応する、実施例1及び実施例2の各試料の番号を示す。
上述の透明支持基板上に、光散乱層を構成する分散液をスピン塗布(500rpm、30秒)にて回転塗布した後、簡易乾燥(80℃、2分)し、さらに、ベーク(120℃、60分)して、膜厚700nmからなる光散乱層を形成した。
分散液は、光散乱層調液として、屈折率2.4、平均粒径0.25μmのTiO2粒子(テイカ(株)製 JR600A)と樹脂溶液(APM社製 ED230AL(有機無機ハイブリッド樹脂))との固形分比率が70vol%/30vol%、n-プロピルアセテートとシクロヘキサノンとの溶媒比が10wt%/90wt%、固形分濃度が15wt%となるように、10ml量の比率で処方設計した。
次に、TiO2分散液を100rpmで撹拌しながら、樹脂を少量ずつ混合添加し、添加完了後、500rpmまで攪拌速度を上げ、10分間混合し、光散乱層塗布液を得た。
その後、疎水性PVDF 0.45μmフィルター(ワットマン社製)にて濾過し、目的の分散液を得た。
試料301~322の構成、並びに、素子反射率差、素子効率向上率、及び、視野角依存性の測定結果を下記表4に示す。
表4に示す結果から、素子反射率差が30%以下の試料では、素子効率向上率が高く、さらに、視野角依存性が小さい結果が得られた。これに対し、素子反射率差が30%を超える試料では、素子効率向上率が低く、視野角依存性が増加する結果が得られた。
従って、この結果から、波長450nm~750nmの光における素子反射率の最大値と最小値との差を30%以下とすることにより、素子効率、及び、視野角依存性に優れた有機EL素子を実現することができる。
この結果から、素子反射率差が30%を超えることにより、有機EL素子の視野角依存性が急激に悪化することがわかる。従って、表4に示す結果から、波長450nm~750nmの光における素子反射率の最大値と最小値との差を30%以下とすることにより、視野角依存性に優れた有機EL素子を実現することができる。
試料401~412の各有機EL素子を、以下に示す手順で作製して評価した。
(基板~陽極)
上述の実施例1の試料102と同様の方法により、透明支持基板上に陽極を形成した。
まず、形成した陽極上に、化合物M-2の入った蒸着用るつぼに通電して加熱し、蒸着速度0.1nm/秒で透明支持基板に蒸着し、膜厚120nmの正孔注入輸送層を形成した。
次に、化合物BD-1及び化合物H-1を、化合物BD-1が5%の濃度になるように蒸着速度0.1nm/秒で共蒸着し、膜厚30nmの青色発光を呈する蛍光発光層を形成した。
そして、化合物E-0を蒸着速度0.1nm/秒で蒸着し、膜厚5nmの正孔阻止層を形成した。
さらに、化合物E-1を蒸着速度0.1nm/秒、フッ化カリウム(KF)0.01nm/秒で共蒸着し、膜厚45nmの電子輸送層を形成した。
次に、アルミニウム、リチウム又はカルシウムを0.05nm/秒で1~4nm製膜し中間層を形成した。
ただし、試料412においては、中間層の形成を行なっていない。
中間層上に化合物M-1を蒸着速度0.1nm/秒で蒸着し、膜厚15nmの正孔注入層を形成した。
さらに、化合物M-2の入った蒸着用るつぼに通電して加熱し、蒸着速度0.1nm/秒で蒸着し、膜厚120nmの正孔注入輸送層を形成した。
次に、化合物E-0を蒸着速度0.1nm/秒で蒸着し、膜厚5nmの正孔阻止層を形成した。
その後、化合物E-1を蒸着速度0.1nm/秒、フッ化カリウム(KF)0.01nm/秒で共蒸着し、膜厚45nmの電子輸送層を形成した。
次に、形成した発光ユニットの電子輸送層上に、銀を蒸着して膜厚100nmの陰極を形成した。
最後に、陰極まで形成した有機EL素子の非発光面をガラスケースで覆い、試料401~412の有機EL素子を作製した。なお、有機EL素子の発光サイズは20×20mmとした。
試料401~412の構成、並びに、素子反射率差、素子効率、及び、視野角依存性の測定結果を下記表5に示す。
表5に示す結果から、素子反射率差が30%以下の試料では、素子効率が高く、さらに、視野角依存性が小さい結果が得られた。これに対し、素子反射率差が30%を超える試料では、素子効率が低下し、視野角依存性が増加する結果が得られた。
従って、この結果から、波長450nm~750nmの光における素子反射率の最大値と最小値との差を30%以下とすることにより、素子効率、及び、視野角依存性に優れた有機EL素子を実現することができる。
さらに、中間層としてLi又はCaを用いて試料では、膜厚が小さい試料の素子反射率差が小さく、膜厚が大きい試料の素子反射率差が大きくなる傾向が見られる。これは、中間層の膜厚が小さくなることにより、中間層の光透過性が向上し、中間層を介した多重反射の発生を抑制することができるためと考えられる。
特に、中間層を設けていない試料412が最も素子反射率差が小さく、素子効率、及び、視野角依存性においても最も良好な結果が得られた。この結果からも、中間層の反射率が低く、光透過性が高い構成とし、特に中間層を設けない構成とすることにより、有機EL素子内での中間層を介した多重反射を抑制することができ、有機EL素子の視野角依存性を向上させることができると考えられる。
試料501~518の各有機EL素子を作製して評価した。
試料501~518の各有機EL素子は、表6に示すように、正孔注入輸送層の膜厚を調整して第1発光ユニットと第2発光ユニットの厚さを変更し、上述の実施例4の試料406又は試料412と同様の手法を用いて作製した。
そして、上述の実施例1と同様の方法で素子反射率差、素子効率、及び、視野角依存性を測定した。なお、量子効率と視野角依存性は、試料401からの相対値として求めた。
表6に示す結果から、素子反射率差が30%以下の試料では、素子効率が高く、さらに、視野角依存性が小さい結果が得られた。これに対し、素子反射率差が30%を超える試料では、素子効率が低下し、視野角依存性が増加する結果が得られた。
さらに、各試料において、第1発光ユニットの厚さと第2発光ユニットの厚さとをそれぞれ変化させても、各試料の発光ユニットの合計の厚さが同じ場合には、同様の結果が得られている。つまり、表6に示す結果からは、素子反射率差は、発光ユニットの合計の厚さに依存することがわかる。
従って、表6に示す結果から、発光ユニット合計の厚さにより各波長の素子反射率差に影響を与えることがわかる。
また、発光ユニットの厚さが各波長の素子反射率差に影響を与えた場合にも、波長450nm~750nmの光における素子反射率の最大値と最小値との差を30%以下とすることにより、素子効率、及び、視野角依存性に優れた有機EL素子を実現することができることがわかる。
試料601~628の各有機EL素子を作製して評価した。
試料601~628は、基板上に下記の光散乱層を形成し、この光散乱層上に陽極を形成した以外は、上述の実施例4の試料401~412、及び、実施例5の501,502,504~511,513~518と同様の手法を用いて作製した。
光散乱層は、上述の実施例3の試料301と同様の手法により形成した。
表7に、試料601~628の有機EL素子の構成に対応する、実施例4及び実施例5の各試料の番号を示す。
試料601~628の構成、並びに、素子反射率差、素子効率向上率、及び、視野角依存性の測定結果を下記表7に示す。
表7に示す結果から、素子反射率差が30%以下の試料では、素子効率向上率が高く、さらに、視野角依存性が小さい結果が得られた。これに対し、素子反射率差が30%を超える試料では、素子効率向上率が低下し、視野角依存性が増加する結果が得られた。
従って、この結果から、波長450nm~750nmの光における素子反射率の最大値と最小値との差を30%以下とすることにより、素子効率、及び、視野角依存性に優れた有機EL素子を実現することができる。
さらに、試料610の素子反射率差が30%であり、試料611の素子反射率差が35%であるが、視野角依存性は試料610が12であるのに対し、試料611では27まで悪化している。
試料613の素子反射率差が29%であり、試料614の素子反射率差が31%であるが、視野角依存性は試料613が12であるのに対し、試料614では23まで悪化している。
試料617の素子反射率差が28%であり、試料618の素子反射率差が31%であるが、視野角依存性は試料617が14であるのに対し、試料618では23まで悪化している。
Claims (8)
- 銀(Ag)を主成分とする透明電極と、金属からなる反射電極と、前記透明電極と前記反射電極との間に設けられた少なくとも1層以上の発光層とを備える有機電界発光素子であって、
波長450nm~750nmの光における素子反射率の最大値と最小値との差が30%以内である
有機電界発光素子。 - 前記透明電極の厚さが4nm以上15nm以下である請求項1に記載の有機電界発光素子。
- 前記反射電極の反射率が90%以上である請求項1に記載の有機電界発光素子。
- 前記透明電極と前記反射電極との間に形成される層の合計の厚さが、波長450nm~750nmの光における素子反射率の最大値と最小値との差が30%以内となるように設定されている請求項1に記載の有機電界発光素子。
- 前記透明電極が窒素原子(N)を含んだ化合物を用いて構成された窒素含有層に接して構成され、当該化合物に含まれる窒素原子(N)が有する非共有電子対のうち芳香族性に関与せずかつ金属に配位していない非共有電子対の数をn、分子量をMとした場合の有効非共有電子対含有率[n/M]が、2.0×10-3≦[n/M]を満たす請求項1に記載の有機電界発光素子。
- 前記透明電極と前記反射電極との間に前記発光層が2層以上積層されている請求項1に記載の有機電界発光素子。
- 前記発光層が、中間層を介して2層以上積層されている請求項6に記載の有機電界発光素子。
- 前記発光層よりも光射出方向側に、光散乱層を備える請求項1に記載の有機電界発光素子。
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US15/038,876 US20160380227A1 (en) | 2014-02-24 | 2015-01-29 | Organic electroluminescent element |
JP2016504015A JPWO2015125581A1 (ja) | 2014-02-24 | 2015-01-29 | 有機電界発光素子 |
KR1020167013968A KR101802683B1 (ko) | 2014-02-24 | 2015-01-29 | 유기 전계 발광 소자 |
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JP2017212042A (ja) * | 2016-05-23 | 2017-11-30 | 株式会社カネカ | 有機el素子 |
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KR102370357B1 (ko) * | 2017-08-16 | 2022-03-07 | 삼성디스플레이 주식회사 | 유기 발광 소자 |
WO2020202284A1 (ja) * | 2019-03-29 | 2020-10-08 | シャープ株式会社 | 表示装置 |
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