WO2011037209A1 - 有機電界発光素子 - Google Patents
有機電界発光素子 Download PDFInfo
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- WO2011037209A1 WO2011037209A1 PCT/JP2010/066601 JP2010066601W WO2011037209A1 WO 2011037209 A1 WO2011037209 A1 WO 2011037209A1 JP 2010066601 W JP2010066601 W JP 2010066601W WO 2011037209 A1 WO2011037209 A1 WO 2011037209A1
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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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/19—Tandem OLEDs
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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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
- H10K50/10—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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/27—Combination of fluorescent and phosphorescent emission
Definitions
- the present invention relates to an organic electroluminescent device, and more particularly to an organic electroluminescent device suitable for white light emission.
- An organic electroluminescence element (organic electroluminescence element) formed by laminating an organic material layer including a light emitting layer in a single layer or a multilayer between electrodes is known.
- This organic electroluminescent element has one electrode as an anode and the other electrode as a cathode. By applying a voltage between both electrodes, electrons injected and transported from the cathode side into the organic material layer are transferred to the anode side. The light is recombined with holes injected and transported from the surface to obtain light emission.
- An organic electroluminescent element is a thin light emitting element capable of obtaining surface light emission, and has recently attracted attention as a light source for various uses and a display unit of a self-luminous thin display device.
- Japanese Patent Application Laid-Open No. 2007-173827 discloses a white organic electroluminescent element including a phosphorescent material that emits red light, a phosphorescent material that emits green light, and a fluorescent material that emits blue light.
- the layer of fluorescent material emitting blue light is a rule, and the chromaticity of light emission of the entire device changes, and the layer of fluorescent blue light emitting material changes in chromaticity. Therefore, there is a problem that the lifetime of the organic electroluminescent element is shortened when viewed from the lifetime due to the amount of change in chromaticity.
- there are various colors such as D, N, W, WW, and L, and these individual white colors are within the range of JIS standards. It was difficult to emit light without changing the chromaticity.
- the present invention has been made in view of the above points, and is an organic electroluminescent device having high luminous efficiency, a long lifetime, and a good balance of light emission, particularly a white light-emitting organic electroluminescent device with high efficiency and long lifetime. Is intended to provide.
- the organic electroluminescent element of the present invention comprises a phosphorescent red light emitting layer 12, a phosphorescent green light emitting layer 11, a fluorescent blue light emitting layer 22, and a fluorescent green light emitting layer 21.
- green light emission is generated by phosphorescence and fluorescence to improve the light emission balance, and the conversion efficiency from electric energy to light can be improved. Since the change in chromaticity can be suppressed, an organic electroluminescent element with high luminous efficiency and long life can be obtained.
- the phosphorescent unit 1 including the phosphorescent red light-emitting layer 12 and the phosphorescent green light-emitting layer 11, the fluorescent light including the fluorescent blue light-emitting layer 22 and the fluorescent green light-emitting layer 21. It is preferable that the phosphor unit 1 and the fluorescent unit 2 are connected via an intermediate layer 3. According to this configuration, since the element can be configured by a two-stage multi-unit, an organic electroluminescent element with higher efficiency and longer life can be obtained.
- the phosphorescent unit 1 including the phosphorescent red light-emitting layer 12 and the phosphorescent green light-emitting layer 11, the fluorescent light including the fluorescent blue light-emitting layer 22 and the fluorescent green light-emitting layer 21. It is preferable that the unit 2, the anode 4 b, and the cathode 4 a are provided, and the phosphorescent unit 1 is disposed on the cathode 4 a side with respect to the fluorescent unit 2. According to this configuration, electrons can be injected into the phosphorescence unit and holes can be injected into the fluorescence unit first, so that the luminous efficiency can be further increased.
- the phosphorescent unit 1 including the phosphorescent red light-emitting layer 12 and the phosphorescent green light-emitting layer 11, the fluorescent light including the fluorescent blue light-emitting layer 22 and the fluorescent green light-emitting layer 21.
- ⁇ GT ⁇ GT/ I ( ⁇ RT)] satisfies I ( ⁇ GT) / I ( ⁇ RT) ⁇ 0.65, and the maximum intensity [I ( ⁇ BS)] of the blue emission wavelength ( ⁇ BS) in the fluorescent unit 2 and green light emission
- the ratio [I ( ⁇ GS) / I ( ⁇ BS)] of the wavelength ( ⁇ GS) to the maximum intensity [I ( ⁇ GS)] preferably satisfies I ( ⁇ GS) / I ( ⁇ BS)> 0.3. According to this configuration, the light emission balance of each unit can be improved, and an organic electroluminescent element with excellent light emission balance and little change in chromaticity can be obtained.
- the phosphorescent unit 1 including the phosphorescent red light emitting layer 12 and the phosphorescent green light emitting layer 11, and the fluorescent unit 2 including the fluorescent blue light emitting layer 22 and the fluorescent green light emitting layer 21.
- the wavelength difference between the green emission wavelength ( ⁇ GT) in the phosphorescent unit 1 and the green emission wavelength ( ⁇ GS) in the fluorescent unit 2 is preferably 10 nm or less in absolute value. According to this configuration, the green wavelength in the phosphorescent unit and the green wavelength in the fluorescent unit are close to each other, so that the luminous efficiency can be increased and the lifetime can be extended, and further, the organic electric field with high efficiency and long lifetime can be achieved. A light emitting element can be obtained.
- the ionization potential (IpB) of the light emitting dopant of the fluorescent blue light emitting layer 22 is larger than the ionization potential (IpG) of the light emitting dopant of the fluorescent green light emitting layer 21, and the light emitting dopant of the fluorescent blue light emitting layer 22.
- the electron affinity (EaB) of the fluorescent green light emitting layer 21 is preferably larger than the electron affinity (EaG) of the light emitting dopant.
- the color mixture of the luminescent color in the phosphorescent red light emitting layer 12, the phosphorescent green light emitting layer 11, the fluorescent blue light emitting layer 22, and the fluorescent green light emitting layer 21 is W color. , WW color, or L color is preferable. According to this configuration, the light emission life can be extended, and an organic electroluminescence device having a longer life can be obtained.
- the maximum intensity (IR) in the red wavelength region, the maximum intensity (IG) in the green wavelength region, and the maximum intensity (IB) in the blue wavelength region are weak in this order.
- IR> IG> IB is preferable.
- the emission intensity is in the order of red, blue, and green, the emission balance can be improved, and a high-efficiency, long-life organic electroluminescence device with excellent emission balance can be obtained. Can do.
- the phosphorescent red light emitting layer 12 includes a phosphorescent red light emitting dopant that emits red phosphorescence, and the phosphorescent red light emitting dopant is bis- (3- (2- (2- (2-pyridyl) benzothienyl) mono-acetylacetonate) iridium (III)), Bis (2-phenylbenzothiazolato) (acetylacetonate) iridium (III) (bis- (2-phenylbenzothiazolate) (acetylacetonate) Iridium Bt 2 Ir (acac)), 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphyrin platinum (II) (2,3,7,8,12,13, It is preferably formed from one substance selected from the group consisting of 17,18-octaethyl-21H, 23H-porphyrin platinum (II) (2,3,7,8,12,13
- the phosphorescent green light-emitting layer 11 includes a phosphorescent green light-emitting dopant that emits green phosphorescence, and the phosphorescent green light-emitting dopant is factory (2-phenylpyridine).
- Iridium Bis (2-phenylpyridine) (acetylacetonate) iridium (III) (Bis- (2phenylpyridine) (acetylacetonato) iridium / Ir (ppy) 2 (acac)), Tris [2- (p-tolyl) pyridine It is preferably formed from one substance selected from the group consisting of] iridium (III) (tris [2- (para-tolyl) pyridine] iridium ⁇ Ir (mppy) 3 ). Thereby, green phosphorescence can be reliably emitted from the phosphorescent green light emitting layer 11.
- the fluorescent blue light emitting layer 22 includes a fluorescent blue light emitting dopant that emits blue fluorescence, and the fluorescent blue light emitting dopant is 1-tert-butyl-perylene (TBP), 4 , 4'-Bis (9-ethyl-3-carbazovinylene) -1,1'-biphenyl (4,4'-bis (9-ethyl-3-carbazovinylene) -1,1'-biphenyl BCzVBi), from perylene
- TBP 1-tert-butyl-perylene
- TBP 1-tert-butyl-perylene
- the fluorescent green light-emitting layer 21 includes a fluorescent green light-emitting dopant that emits green fluorescence, and the fluorescent green light-emitting dopant includes 2,3,6,7-Tetrahydro-1, 1,7,7, -tetramethyl-1H, 5H, 11H-10- (2-benzothiazolyl) quinolizino- [9,9a, 1gh] coumarin (2,3,6,7-tetrahydro-1,1,7,7 , -Tetramethyl-1H, 5H, 11H-10 (2-benzothiazolyl) quinolidino- [9,9a, 1gh] coumarin / C545T), N, N′-Dimethyl-quinacridone (N, N′-dimethyl-quinacridone / DMQA) ), Coumarin 6 and rubrene, and is preferably formed from one substance selected from the group consisting of rubrene.
- the host incorporating the fluorescent green light emitting dopant is tris (8-oxoquinoline) aluminum (III), 9,10-Di- (2naphthyl) anthracene (9,10-di- (2-naphthyl) anthracene / ADN). ), Bis (9,9′-diarylfluorene) (bis (9,9′-diarylfluorene) ⁇ BDAF).
- the doping concentration of the fluorescent green light-emitting dopant is preferably 1 to 20% by mass. Thereby, green fluorescence can be reliably emitted from the fluorescent green light emitting layer 21.
- FIG. 6 It is a schematic sectional drawing which shows an example of embodiment of the organic electroluminescent element of this invention.
- 6 is a graph showing emission spectra of Examples 1 to 5.
- 6 is a graph showing emission spectra of Comparative Examples 1 to 5.
- 6 is a graph showing emission spectra of Examples 6 to 10.
- a and B are graphs showing an emission spectrum of an evaluation element for explaining the present invention.
- A is a potential diagram for explaining the energy levels of Examples 1 to 5 and B is for Examples 11 to 15.
- FIG. It is a graph which shows the emission spectrum of rubrene.
- FIG. 1 shows an example of an embodiment of the organic electroluminescent element of the present invention.
- This organic electroluminescent element is configured by laminating each layer between a pair of electrodes 4 and 4 on the surface of a substrate 5 such as a glass substrate.
- the organic electroluminescent element includes a phosphorescent red light emitting layer 12, a phosphorescent green light emitting layer 11, a fluorescent blue light emitting layer 22, and a fluorescent green light emitting layer 21. Accordingly, the emission color is formed by phosphorescence exhibiting red and green and fluorescence exhibiting blue and green. In this way, phosphorescence and fluorescence are used to emit light, and in particular, green light emission is generated by two types of phosphorescence and fluorescence. Become good.
- the conversion efficiency from electrical energy to light can be improved, and changes in luminance and chromaticity can be suppressed even when light is emitted for a long time. That is, since the luminance life of green light emission is extended by the lamination of two green light emitting layers of phosphorescent green and fluorescent green, as a result, the change in chromaticity is reduced and the life can be prolonged.
- the substrate 5 supports the organic electroluminescent element and is formed of a material such as a glass substrate. In order to take out the emitted light from the substrate 5 side, the substrate 5 is preferably a transparent substrate.
- the electrode 4 is formed of a material such as a conductive metal, and one is a cathode 4a and the other is an anode 4b.
- the anode 4 b is formed as a layer in contact with the substrate 5.
- the anode 4b is formed as a transparent electrode so that light is extracted from at least the substrate 5 side. It has become.
- the cathode 4a may be a transparent electrode, and light may be extracted from the cathode 4a side, or light may be extracted from both sides of the electrodes 4 and 4.
- the phosphorescent red light emitting layer 12 and the phosphorescent green light emitting layer 11 are formed as layers in contact with each other.
- the phosphorescent red light emitting layer 12 is disposed on the anode 4b side
- the phosphorescent green light emitting layer 11 is disposed on the cathode 4a side.
- the phosphorescent unit 1 is composed of the two phosphorescent light emitting layers.
- the phosphorescent light-emitting layers are formed by doping the host material of the light-emitting layer with a phosphorescent dopant at an appropriate concentration. At this time, if a red light emitting dopant is used as the light emitting dopant, the phosphorescent red light emitting layer 12 is obtained, and if a green light emitting dopant is used, the phosphorescent green light emitting layer 11 is obtained.
- the fluorescent blue light emitting layer 22 and the fluorescent green light emitting layer 21 are formed as layers in contact with each other.
- the fluorescent blue light emitting layer 22 is disposed on the anode 4b side
- the fluorescent green light emitting layer 21 is disposed on the cathode 4a side.
- the two fluorescent light emitting layers constitute a fluorescent unit 2.
- the fluorescent light emitting layer (fluorescent blue light emitting layer 22 and fluorescent green light emitting layer 21) is formed by doping a host material of the light emitting layer with a fluorescent light emitting dopant at an appropriate concentration. In that case, if a blue light emission dopant is used as a light emission dopant, the fluorescence blue light emission layer 22 will be obtained, and if a green light emission dopant is used, the fluorescence green light emission layer 21 will be obtained.
- An intermediate layer 3 is formed between the phosphorescent unit 1 and the fluorescent unit 2.
- the intermediate layer 3 is formed of a conductive material such as a metal compound or a mixture of a metal compound and an organic material, and smoothly moves electrons and holes between the light emitting units.
- the phosphorescence unit 1 and the fluorescence unit 2 are electrically connected in series via the intermediate layer 3. That is, the phosphorescence unit 1, the intermediate layer 3, and the fluorescence unit 2 are arranged between the electrodes 4 and 4 in series, not in parallel.
- Such an element structure is called a two-stage multi-unit. Thereby, since electrons and holes flow in each light emitting layer without any bias, light emission with a good balance can be obtained, and high efficiency and long life can be obtained. Moreover, if it comprises a two-stage multi-unit, lamination can be facilitated and productivity can be improved.
- the intermediate layer 3 may be a single layer or a plurality of layers.
- a single layer simplifies the device configuration and facilitates manufacturing.
- a layer material suitable for electron transport and hole transport to each light-emitting unit can be adopted, and further improvement in efficiency and longer life can be achieved.
- the phosphorescence unit 1 is arranged on the cathode 4a side and the fluorescence unit 2 is arranged on the anode 4b side. That is, electrons are injected into the phosphorescence unit 1 and holes are injected into the fluorescence unit 2 first.
- the light emission efficiency is further increased.
- the phosphorescent unit 1 is arranged on the anode 4b side and the fluorescent unit 2 is arranged on the cathode 4a side, the lifetime can be extended, but the luminous efficiency is lowered, which is not preferable.
- an organic electroluminescence element can observe an emission spectrum in the visible light region (wavelength: about 400 to 800 nm) by using an optical device such as a spectral radiance meter (see the emission spectrum in FIG. 2).
- This emission spectrum relatively indicates the intensity of light emission at each wavelength.
- the blue light emitting dopant having the maximum light emission intensity in the blue wavelength region (wavelength: about 450 to 490 nm) and the maximum light emission intensity in the green wavelength region (wavelength: about 500 to 570 nm).
- An organic electroluminescent device is configured using a green light emitting dopant having a red light emitting dopant having a maximum light emission intensity in a red wavelength region (wavelength: about 590 to 650 nm). That is, by combining the three primary colors of red, green, and blue, various emission colors can be obtained, and in particular, white emission can be obtained.
- the color of the luminescent dopant in the present invention is defined from the value of the wavelength having the maximum luminescence intensity as described above. Depending on the spread of the emission spectrum, the color may become unclear or may have a different color, but the emission color is defined only by the above wavelength.
- the luminescent dopant rubrene is yellow light emission (or yellow-green light emission) and can be called a yellow light emission dopant. This is because the emission spectrum broadens to the long wavelength side. Since the maximum emission wavelength is around 560 nm, it is classified as a green emission dopant.
- an emission spectrum of rubrene is shown in FIG.
- JIS standard color temperature
- D Daylight color: 5700-7100K: Color of sunlight at noon in fine weather
- N White color: 4600-5400K: Color of sunlight in the time zone between noon in fine weather
- W White: 3900-4500K: Color of sunlight 2 hours after sunrise
- WW Warm white: 3200-3700K: Color of evening sunlight
- L Light bulb color: 2600-3150K: Color of white light bulb
- JIS standard Is “Classification by JIS Z 9112 fluorescent lamp light source color and color rendering”.
- the unit of color temperature “K” is “Kelvin”.
- the organic electroluminescent element by this invention can make the light emission balance of red (R), green (G), blue (B) favorable by the above structures, and was excellent in JIS standard. Since white light emission can be obtained, it is particularly suitable for white light emission.
- the phosphorescent unit 1 when the wavelength at which the emission intensity in the red emission region is maximum is the red emission wavelength ( ⁇ RT) and the wavelength at which the emission intensity in the green emission region is maximum is the green emission wavelength ( ⁇ GT)
- the relationship (ratio) between the maximum intensity [I ( ⁇ GT)] at the red emission wavelength ( ⁇ RT) and the maximum intensity [I ( ⁇ GT)] at the green emission wavelength ( ⁇ GT) satisfies the following equation: Is preferred.
- the wavelength at which the emission intensity in the blue emission region is maximized is the blue emission wavelength ( ⁇ BS)
- the wavelength at which the emission intensity in the green emission region is maximum is the green emission wavelength green emission wavelength ( ⁇ GS)
- the relationship (ratio) between the maximum intensity [I ( ⁇ BS)] at the blue emission wavelength ( ⁇ BS) and the maximum intensity [I ( ⁇ GS)] at the green emission wavelength ( ⁇ GS) is It is preferable to satisfy the formula:
- the relative intensity of each luminescent color has the above-mentioned numerical relationship, so that the emission balance in each unit of green and red in the phosphorescent unit 1 and blue and green in the fluorescent unit 2 is good. Can be. If the above relationship is not satisfied, the light emission balance is lowered, and a desired light emission color may not be obtained. If the relationship between the spectral intensities is as described above, the light emission that falls within the white range defined in the JIS standard is maintained without change, and the element has a high efficiency and a long life.
- the wavelength difference between the green emission wavelength ( ⁇ GT) in the phosphorescence unit 1 and the green emission wavelength ( ⁇ GS) in the fluorescence unit 2 is preferably 10 nm or less in absolute value. That is, the relationship is
- the ionization potential (IpB) of the light emitting dopant (blue light emitting dopant) of the fluorescent blue light emitting layer 22 is preferably larger than the ionization potential (IpG) of the light emitting dopant (green light emitting dopant) of the fluorescent green light emitting layer 21. That is, IpB> IpG.
- the electron affinity (EaB) of the light emitting dopant (blue light emitting dopant) of the fluorescent blue light emitting layer 22 is preferably larger than the electron affinity (EaG) of the light emitting dopant (green light emitting dopant) of the fluorescent green light emitting layer 21. That is, the relationship EaB> EaG.
- the emission level of the fluorescent blue light-emitting layer 22 is higher than that of the fluorescent green light-emitting layer 21 in terms of both the ionization potential (Ip) and the electron affinity (Ea).
- Ip ionization potential
- Ea electron affinity
- the light emission color is one of W color (white), WW color (warm white), and L color (bulb color) among the above-described white types.
- W color white
- WW color warm white
- L color bulb color
- the light emission lifetime can be further extended, and a long-life organic electroluminescence device can be obtained. That is, as described above, although there are various emission colors even if it is white light emission, the conventional organic electroluminescence device cannot sufficiently prevent a minute change in chromaticity, and the color of the white emission color due to the change in chromaticity. It was difficult to maintain the taste.
- the organic electroluminescent device according to the present invention in particular, if the emission color is W, WW, or L, the chromaticity change is small and the color of white light emission can be maintained and the lifetime can be extended. It is.
- the maximum intensity (IR) in the red wavelength region, the maximum intensity (IG) in the green wavelength region, and the maximum intensity (IB) in the blue wavelength region are in this order. It is preferable to become weak. That is, IR> IG> IB. Thereby, the light emission balance becomes good, and a high-efficiency and long-life organic electroluminescence device with excellent light emission balance can be obtained.
- a hole injection layer 31 and a hole transport layer 32 are laminated in this order between the anode 4b and the fluorescent unit 2.
- An electron transport layer 33 is laminated between the fluorescent unit 2 and the intermediate layer 3.
- a hole transport layer 34 is laminated between the intermediate layer 3 and the phosphorescent unit 1.
- An electron transport layer 35 and an electron injection layer 36 are laminated in this order between the phosphorescence unit 1 and the cathode 4a.
- the layer configuration (stacking order) of the organic electroluminescent element is not limited to the form shown in FIG.
- the stacking order from the lower side of the figure is the substrate 5, anode 4 b, fluorescent unit 2, intermediate layer 3, phosphorescent unit 1.
- the cathode 4a is in this order, but the reverse order may be the substrate 5, the cathode 4a, the phosphor unit 1, the intermediate layer 3, the fluorescent unit 2, and the anode 4b.
- the thickness of the phosphorescent red light emitting layer 12 is about 5 to 40 nm
- the thickness of the phosphorescent green light emitting layer 11 is about 5 to 40 nm
- the thickness of the fluorescent blue light emitting layer 22 is 5 nm.
- the film thickness of the fluorescent green light emitting layer 21 can be set to about 5 to 40 nm.
- the film thickness ratio of the phosphorescent red light emitting layer 12 and the phosphorescent green light emitting layer 11 is about 1: 8 to 8: 1, and the film thickness of the fluorescent blue light emitting layer 22 and the fluorescent light emitting layer 22 are fluorescent.
- the film thickness of the green light emitting layer 21 can be set to about 1: 8 to 8: 1, and the film thickness of the fluorescent unit 2 and the film thickness of the phosphorescent unit 1 can be set to about 1: 3 to 3: 1. can do.
- the film thickness of the intermediate layer 3 can be set to about 3 to 50 nm.
- the material of the anode 4b include metals such as gold, conductive materials such as CuI, ITO (indium-tin oxide), SnO 2 , ZnO, IZO (indium-zinc oxide), PEDOT, and polyaniline.
- a conductive polymer doped with a polymer and an optional acceptor, a conductive light-transmitting material such as a carbon nanotube, or the like can be used.
- the electrode material which consists of a metal, an alloy, an electroconductive compound, and these mixtures with a small work function for the other electrode 4 (cathode 4a).
- the material of the cathode 4a include alkali metals, alkaline earth metals, and the like, and alloys thereof with other metals such as sodium, sodium-potassium alloy, lithium, magnesium, magnesium-silver mixture, magnesium-indium mixture.
- An aluminum-lithium alloy can be mentioned as an example.
- one or more conductive materials such as metals may be laminated and used.
- an alkali metal / Al laminate, an alkaline earth metal / Al laminate, an alkaline earth metal / Ag laminate, a magnesium-silver alloy / Ag laminate, and the like can be given as examples.
- CBP, CzTT, TCTA, mCP, CDBP, or the like can be used as a host of the light emitting layer.
- Ir (ppy) 3 , Ir (ppy) 2 (acac), Ir (mppy) 3, or the like can be used as the phosphorescent green light-emitting dopant.
- the dope concentration is usually 1 to 40% by mass.
- CBP, CzTT, TCTA, mCP, CDBP or the like can be used as a host of the light emitting layer.
- phosphorescent red light emitting dopant Btp 2 Ir (acac), Bt 2 Ir (acac), PtOEP, or the like can be used.
- the dope concentration is usually 1 to 40% by mass.
- Alq 3 , ADN, BDAF, or the like can be used as a host of the light emitting layer.
- the fluorescent green light-emitting dopant C545T, DMQA, coumarin 6, rubrene, or the like can be used.
- the dope concentration is usually 1 to 20% by mass.
- TBADN, ADN, BDAF, or the like can be used as a host of the light emitting layer.
- TBP, BCzVBi, perylene, or the like can be used as the fluorescent blue light-emitting dopant, and NPD, TPD, Spiro-TAD, or the like can be used as the charge transfer assisting dopant.
- the total doping concentration of the luminescent dopant and the charge transfer assisting dopant is usually 1 to 30% by mass.
- the intermediate layer 3 BCP: Li, ITO, NPD: MoO 3 , Liq: Al, or the like can be used.
- the intermediate layer 3 is made of ITO with the first layer made of BCP: Li on the anode 4 b side.
- the second layer can be of a two-layer configuration in which the second layer is disposed on the cathode 4a side.
- hole injection layer 31 CuPc, MTDATA, TiOPC, or the like can be used.
- TPD hole transport layers 32 and 34
- NPD NPD
- TPAC TASi
- DTASi DTASi
- BCP As the electron transport layers 33 and 35, BCP, TAZ, BAlq, Alq 3 , OXD7, PBD, or the like can be used.
- the electron injection layer 36 in addition to fluorides, oxides, and carbonates of alkali metals and alkaline earth metals such as LiF, Li 2 O, MgO, and Li 2 CO 3 , lithium, sodium, cesium, A layer doped with an alkali metal such as calcium or an alkaline earth metal can be used.
- Bt 2 Ir (acac) represents Bis (2-phenylbenzothiazolato) (acetylacetonate) iridium (III) (bis- (2-phenylbenzothiazolate) (acetylacetonato) iridium)
- PtOEP is 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphyrin platinum (II) (2,3,7,8,12,13,17,18-octaethyl-21H , 23H-porphyrin platinum)
- Ir (ppy) 2 (acac) represents Bis (2-phenylpyridine) (acetylacetonate) iridium (III) (bis- (2 phenylpyridine) (acetylacetonato) iridium)
- Ir (mppy) 3 represents Tris [2- (p-tolyl) pyridine] iridium (III) (tris [2- (para
- An organic electroluminescent element can be obtained by laminating each layer using the above materials. Note that a vacuum deposition method, a sputtering method, or the like can be used as a lamination method.
- ITO indium-tin oxide
- the anode 4b having a sheet resistance of 10 ⁇ / ⁇ , thereby producing a glass substrate with ITO.
- This glass substrate with ITO was subjected to ultrasonic cleaning with acetone, pure water and isopropyl alcohol for 15 minutes, then dried and UV ozone cleaned.
- the glass substrate with ITO was set in a vacuum vapor deposition apparatus, and each organic layer or inorganic layer was sequentially heated by resistance heating at a vacuum degree of 5 ⁇ 10 ⁇ 5 Pa or less.
- Al was vapor-deposited to form the cathode 4a.
- Example 5 (Device structure of organic electroluminescence device) (Examples 1 to 5)
- the device structure (layer structure) and the film thickness of each layer are shown below.
- the layer structure of Examples 1 to 5 is the same as that in the form of FIG. However, the intermediate layer 3 is composed of two layers, a first layer and a second layer.
- Substrate 5 Glass substrate (0.7mm) Anode 4b: ITO (150nm) Hole injection layer 31: CuPc (30nm) Hole transport layer 32: TPD (30nm) Fluorescent blue light emitting layer 22: TBADN: TBP: NPD (Xnm) Fluorescent green light-emitting layer 21: Alq 3: C545T (Ynm ) Electron transport layer 33: BCP (30nm) Intermediate layer 3 (first layer): BCP: Li (10 nm) Intermediate layer 3 (second layer): ITO (10 nm) Hole transport layer 34: TPD (30nm) Phosphorescent red light emitting layer 12: CBP: Btp 2 Ir (acac) ( ⁇ nm) Phosphorescent green light emitting layer 11: CBP: Ir (ppy) 3 ( ⁇ nm) Electron transport layer 35: BCP (20nm) Electron injection layer 36: LiF (1 nm) Cathode 4a: Al (80 nm) The details of each light
- the fluorescent blue light-emitting layer 22 is obtained by doping the light-emitting layer host: TBADN with 1.5% blue light-emitting dopant: TBP and 5% with charge transfer auxiliary dopant: NPD.
- the fluorescent green light emitting layer 21 is obtained by doping a light emitting layer host: Alq 3 with a green light emitting dopant: C545T by 1.5%.
- the phosphorescent red light emitting layer 12 is obtained by doping the light emitting layer host: CBP with 10% red light emitting dopant: Btp 2 Ir (acac).
- the phosphorescent green light emitting layer 11 is obtained by doping a light emitting layer host: CBP with 10% of a green light emitting dopant: Ir (ppy) 3 .
- the unit “%” of the dope concentration is “mass%”.
- the film thicknesses X, Y, ⁇ , and ⁇ of each light emitting layer are as shown in Table 1.
- Example 6 to 10 In the organic electroluminescent elements in Examples 1 to 5, the organic electroluminescent elements in Examples 6 to 10 were the same as in Examples 1 to 5 except that the fluorescent green light emitting layer 21 of the fluorescent unit 2 was configured as follows. Configured.
- Fluorescent green light-emitting layer 21 Alq 3: rubrene (Ynm )
- the fluorescent green light-emitting layer 21 is obtained by doping a light-emitting layer host: Alq 3 with a green light-emitting dopant: rubrene (2%).
- this fluorescent green light emitting layer 21 uses rubrene which exhibits yellow light emission in appearance, and can also be called a fluorescent yellow light emitting layer.
- the film thickness is as shown in Table 1.
- Example 11 to 15 In the organic electroluminescent elements in Examples 1 to 5, the organic electroluminescent elements in Examples 11 to 15 were the same as in Examples 1 to 5 except that the fluorescent green light emitting layer 21 of the fluorescent unit 2 was configured as follows. Configured.
- Fluorescent green light-emitting layer 21 Alq 3: coumarin6 (Ynm )
- the film thickness is as shown in Table 1.
- Example 16 The device structure (layer structure) of Example 16 and the film thickness of each layer are shown below.
- Substrate 5 Glass substrate (0.7mm)
- Anode 4b ITO (150nm)
- Hole injection layer 31 CuPc (30nm)
- Hole transport layer 32 TPD (30nm)
- Phosphorescent red light emitting layer 12 CBP: btp 2 Ir (acac) (30nm)
- Phosphorescent green light emitting layer 11 CBP: Ir (ppy) 3 (10nm)
- Hole transport layer 34 TPD (30nm)
- Electron transport layer 35 BCP (20nm)
- Each organic electroluminescent element was connected to a power source (KEYTHLEY 2400), a constant current having a current density of 10 mA / cm 2 was applied, and power efficiency was measured using an integrating sphere (SLMS-CDS manufactured by Labsphere).
- each organic electroluminescence device Connect each organic electroluminescence device to a power supply (KEYTHLEY2400), and apply a constant current of 10 mA / cm 2 current density, and observe the luminance when continuously emitting light using a luminance meter (LS-110 manufactured by Konica Minolta). Then, the half-time when the luminance was reduced by half was measured. At the same time, the change in emission chromaticity was observed, and the color change time when the chromaticity change amount was 0.01 or more was measured compared with the initial emission chromaticity. Of the time when the luminance is reduced by half (half time) and the time when the chromaticity change amount is 0.01 or more (color change time), the shorter time is defined as the lifetime of the element.
- FIG. 2 shows emission spectra of the organic electroluminescent elements of Examples 1 to 5.
- FIG. 3 shows emission spectra of the organic electroluminescent elements of Comparative Examples 1 to 5. Each emission spectrum is normalized by setting the maximum emission intensity in the red wavelength region to “1”.
- Table 2 shows the results (efficiency / lifetime) of comparing the examples and comparative examples for each luminescent color, together with the luminescent colors and CIE chromaticity coordinates of the examples and comparative examples.
- the efficiency and lifetime value of the example in the same luminescent color is set to “1”
- the efficiency and lifetime of the comparative example are shown as relative values (for example, comparative example 1 is compared with example 1).
- the CIE chromaticity coordinates accurately mean “x and y coordinate values in the CIE1931 chromaticity diagram”.
- the x-coordinate value in the CIE 1931 chromaticity diagram is described as “CIE-x”
- the y-coordinate value in the CIE 1931 chromaticity diagram is described as “CIE-y”.
- the emission color can be expressed by the x, y coordinate values in the CIE1931 chromaticity diagram, and the x and y coordinate values of the examples and comparative examples in the emission colors (D to L colors) in Table 2 are close. This means that they exhibit substantially the same emission color.
- D color even if it is simply referred to as D color, since the range called D color is wide, even an organic electroluminescence device exhibiting the same external quantum efficiency is designed to exhibit a greenish emission color (above the black body locus). As a result, the current efficiency (power efficiency) increases due to the visual efficiency.
- the coordinate values in the CIE1931 chromaticity diagram it is possible to show not only the color but also the stricter “same luminescent color”, and it is more possible to compare the efficiency and lifetime in the same luminescent color. It will be possible.
- Example 3 W color
- Example 4 WW color
- Example 5 L color
- Table 3 shows the relative relationship between the maximum emission intensity (IR) in the red wavelength range, the maximum emission intensity (IG) in the green wavelength range, and the maximum emission intensity (IB) in the blue wavelength range in Examples 1 to 5. Indicates strength.
- the wavelengths indicating the maximum emission intensity of each color are as follows.
- Example 16 in which the fluorescent unit 2 is arranged on the cathode 4a side and the phosphorescent unit 1 is arranged on the anode 4b side has the same life but is less efficient than Example 4. It was. That is, it was confirmed that Example 4 in which the phosphorescent unit 1 was arranged on the cathode 4a side was highly efficient.
- the element for each light emitting unit used in Examples 1 to 5 was produced as an evaluation element.
- the layer structure of the evaluation element and the film thickness of each layer are shown below.
- ⁇ Fluorescent unit evaluation element Evaluation elements 1 to 5> Substrate 5: Glass substrate (0.7mm) Anode 4b: ITO (150nm) Hole injection layer 31: CuPc (30nm) Hole transport layer 32: TPD (30nm) Fluorescent blue light emitting layer 22: TBADN: TBP: NPD (Xnm) Fluorescent green light-emitting layer 21: Alq 3: C545T (Ynm ) Electron transport layer 33: BCP (30nm) Electron injection layer 36: LiF (1 nm) Cathode 4a: Al (80 nm) ⁇ Phosphorescence unit evaluation element: Evaluation elements 6 to 10> Substrate 5: Glass substrate (0.7mm) Anode 4b: ITO (150nm) Hole injection layer 31: CuPc (30nm) Hole transport layer 34: TPD (30nm) Phosphorescent red light emitting layer 12: CBP: btp 2 Ir (acac) ( ⁇ nm) Phos
- FIG. 5A shows an emission spectrum of evaluation element 1 which is a fluorescent unit evaluation element
- FIG. 5B shows an emission spectrum of evaluation element 6 which is a phosphorescence unit evaluation element.
- Table 5 shows the relative light emission intensity of each evaluation element.
- the maximum emission intensity in the blue wavelength region is set to “1”, and the maximum emission intensity in the green wavelength region is shown as the relative intensity.
- the maximum emission intensity in the red wavelength region is “1”, and the maximum emission intensity in the green wavelength region is shown as the relative intensity.
- the unit of the film thickness in Table 5 is nm.
- Example 17 and 18 For reference, the light emission characteristics of Examples 17 and 18 and their evaluation elements 11 to 14 having the same layer structure as in Examples 1 to 5 and the film thicknesses shown in Table 6 were examined.
- the film thickness of Example 17 is described in evaluation elements 11 and 13
- the film thickness of Example 18 is described in evaluation elements 12 and 14.
- the results are shown in Table 6.
- Table 7 shows the results of the characteristic evaluation comparing the organic electroluminescent elements of Examples 6 to 10 and Examples 1 to 5.
- FIG. 4 shows emission spectra of the organic electroluminescent elements of Examples 6 to 10.
- Table 8 shows a comparison of energy levels of the light-emitting dopants used in Examples 1 to 5 and Examples 11 to 15.
- Table 9 shows a comparison of efficiency and life between Examples 1 to 5 and Comparative Examples 11 to 15.
- 6A and 6B show diagrams comparing the potential levels of the energy levels of Examples 1 to 5 and the energy levels of Examples 11 to 15, respectively.
- TBP which is the light emitting dopant of the fluorescent blue light emitting layer 22
- C545T which is the light emitting dopant of the fluorescent green light emitting layer 21
- IpB ionization potential
- IpG ionization potential
- EaB electron affinity
- Ip represents the ionization potential
- Ea represents the electron affinity
- each unit is eV.
- TBP which is the light emitting dopant of the fluorescent blue light emitting layer 22
- coumarin6 which is the light emitting dopant of the fluorescent green light emitting layer 21
- TBP has an ionization potential (IpB) of ⁇ 5.5 eV. It is smaller than the ionization potential (IpG) of coumarin6-5.4 eV.
- TBP has an electron affinity (EaB) of ⁇ 2.7 -eV, which is equal to coumarin6's electron affinity (EaG) of ⁇ 2.7 eV.
- FIG. 6 (a) shows the relationship of Examples 1 to 5 and FIG. 6 (b) shows the relationship of Examples 11 to 15 for such energy level relationships.
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Abstract
Description
表示:名称 :JIS規格(色温度):色の説明
D :昼光色: 5700~7100K :晴天の正午の日光の色
N :昼白色: 4600~5400K :晴天の正午をはさんだ時間帯の日光の色
W :白色 : 3900~4500K :日の出2時間後の日光の色
WW:温白色: 3200~3700K :夕方の日光の色
L :電球色: 2600~3150K :白色電球の色
なお、上記において、JIS規格は、「JIS Z 9112 蛍光ランプの光源色及び演色性による区分」である。また、色温度の単位「K」は「ケルビン」である。
それと同時に、蛍光ユニット2においては、青色発光領域での発光強度が最大となる波長を青色発光波長(λBS)とし、緑色発光領域での発光強度が最大となる波長を緑色発光波長緑色発光波長(λGS)としたときに、青色発光波長(λBS)での最大強度[I(λBS)]と、緑色発光波長(λGS)での最大強度[I(λGS)]との関係(比)が、次の式を満たすことが好ましい。
このように、各発光色の相対強度が上記の数値関係になることにより、リン光ユニット1における緑色と赤色、蛍光ユニット2における青色と緑色、の各発光色の各ユニットでの発光バランスを良好にすることができる。上記の関係を満たさないと発光バランスが低下し、所望の発光色を得られなくなるおそれがある。そして、スペクトル強度の関係が上記のようになれば、JIS規格に規定される白色範囲に入る発光が変化することなく維持され、高効率・長寿命の素子になるものである。
ことができる。
Bt2Ir(acac)は、Bis(2-phenylbenzothiazolato)(acetylacetonate)iridium(III)(ビス‐(2‐フェニルベンゾチアゾレート)(アセチルアセトナート)イリジウム)を表し、
PtOEPは、2,3,7,8,12,13,17,18-octaethyl―21H,23H―porphyrin platinum(II)(2,3,7,8,12,13,17,18-オクタエチル‐21H,23H‐ポルフィリン白金)を表し、
Ir(ppy)2(acac)は、Bis(2―phenylpyridine)(acetylacetonate)iridium(III)(ビス‐(2フェニルピリジン)(アセチルアセトナート)イリジウム)を表し、
Ir(mppy)3は、Tris[2―(p―tolyl)pyridine]iridium(III)(トリス[2‐(パラ‐トリル)ピリジン]イリジウム)を表し、
BCzVBiは、4,4'―Bis(9―ethyl―3―carbazovinylene)―1,1'―biphenyl(4,4‘‐ビス(9‐エチル‐3‐カルバゾビニレン)‐1,1’‐ビフェニル)を表し、
TPDは、N, N‘-Bis(3-methylphenyl)-N,N’-bis(phenyl)-benzidine(N,N’-ビス(3-メチルフェニル)-N,N’-ビス(ビフェニル)-ベンジダイン)を表し、
Spiro-TADは、N,N‘-Bis(3-methylphenyl)-N,N’-bis(phenyl)-9,9-spirobifluorene(N,N’-ビス(3メチルフェニル)-N,N’-ビス(ビフェニル)-9,9-スピロビフルオレン)を表し、
C545Tは、2,3,6,7-Tetrahydro-1,1,7,7,-tetramethyl-1H,5H,11H-10―(2-benzothiazolyl)quinolizino―[9,9a,1gh]coumarin(2,3,6,7‐テトラヒドロ-1,1,7,7,-テトラメチル-1H,5H,11H-10(2-ベンゾチアゾリル)キノリジノ-[9,9a,1gh]クマリン)を表し、
DMQAは、N,N‘-Dimethyl-quinacridone(N,N’―ジメチル―キナクリドン)を表し、
ADNは、9,10-Di-(2naphthyl)anthracene(9,10-ジ-(2-ナフチル)アントラセン)を表し、
BDAFは、bis(9,9'-diarylfluorene)(ビス(9,9’-ジアリルフルオレン)を表し、
CBPは、4,4’-N,N’-ジカルバゾールビフェニルを表し、
Alq3は、トリス(8-オキソキノリン)アルミニウム(III)を表し、
TBADNは、2-t-ブチル-9,10-ジ(2-ナフチル)アントラセンを表し、
Ir(ppy)3は、ファクトリス(2-フェニルピリジン)イリジウムを表し、
Btp2Ir(acac)は、ビス-(3-(2-(2-ピリジル)ベンゾチエニル)モノ-アセチルアセトネート)イリジウム(III))を表し、
C545Tは、クマリンC545Tのことであり、10-2-(ベンゾチアゾリル)-2,3,6,7-テトラヒドロ-1,1,7,7-テトラメチル-1H,5H,11H-(1)ベンゾピロピラノ(6,7,-8-ij)キノリジン-11-オンを表し、
TBPは、1-tert-ブチル-ペリレンを表し、
NPDは、4,4’-ビス[N-(ナフチル)-N-フェニル-アミノ]ビフェニルを表し、
BCPは、2,9-ジメチル-4,7-ジフェニル-1,10-フェナンスロリンを表し、
CuPcは、銅フタロシアニンを表し、
TPDは、N,N’-ビス(3-メチルフェニル)-(1,1’-ビフェニル)-4,4’-ジアミンを表している。
各実施例及び比較例の有機電界発光素子の作製を次の手順で行った。
(実施例1~5)
以下に、デバイス構造(層構成)と各層の膜厚を示す。実施例1~5の層構成については、図1の形態と同じである。ただし、中間層3は第1層と第2層との二つの層で構成されている。
基板5 : ガラス基板(0.7mm)
陽極4b : ITO (150nm)
正孔注入層31 : CuPc (30nm)
正孔輸送層32 : TPD (30nm)
蛍光青色発光層22 : TBADN:TBP:NPD (Xnm)
蛍光緑色発光層21 : Alq3:C545T (Ynm)
電子輸送層33 : BCP (30nm)
中間層3(第1層) : BCP:Li (10nm)
中間層3(第2層) : ITO (10nm)
正孔輸送層34 : TPD (30nm)
リン光赤色発光層12: CBP:Btp2Ir(acac) (αnm)
リン光緑色発光層11: CBP:Ir(ppy)3 (βnm)
電子輸送層35 : BCP (20nm)
電子注入層36 : LiF (1nm)
陰極4a : Al (80nm)
上記の有機電界発光素子において、各発光層の詳細を次に示す。
以下に、比較例1~5のデバイス構造(層構成)と各層の膜厚を示す。
基板5 : ガラス基板(0.7mm)
陽極4b : ITO (150nm)
正孔注入層31 : CuPc (30nm)
正孔輸送層32 : TPD (30nm)
蛍光青色発光層22 : TBADN:TBP:NPD (Xnm)
電子輸送層33 : BCP (30nm)
中間層3(第1層) : BCP:Li (10nm)
中間層3(第2層) : ITO (10nm)
正孔輸送層34 : TPD (30nm)
リン光赤色発光層12: CBP:btp2Ir(acac) (αnm)
リン光緑色発光層11: CBP:Ir(ppy)3 (βnm)
電子輸送層35 : BCP (20nm)
電子注入層36 : LiF (1nm)
陰極4a : Al (80nm)
比較例の有機電界発光素子は、実施例の有機電界発光素子から蛍光緑色発光層21を除去した構成となっており、特許文献1の層構成の考え方に近いものである。ただし、発光色の調整のため、各発光層の膜厚を調整している。なお、各発光層の詳細は実施例と同様であり、各発光層の膜厚X、α、βについては、表1に示す通りである。
実施例1~5における有機電界発光素子において、蛍光ユニット2の蛍光緑色発光層21を以下の構成とした以外は、実施例1~5と同様に、実施例6~10の有機電界発光素子を構成した。
蛍光緑色発光層21は、発光層ホスト:Alq3に、緑発光ドーパント:rubrene(ルブレン)を2%ドープしたものである。なお、この蛍光緑色発光層21は、見た目には黄色発光を呈するrubreneを用いており、蛍光黄色発光層とも呼べる。また、膜厚については、表1に示すとおりである。
実施例1~5における有機電界発光素子において、蛍光ユニット2の蛍光緑色発光層21を以下の構成とした以外は、実施例1~5と同様に、実施例11~15の有機電界発光素子を構成した。
蛍光緑色発光層21は、発光層ホスト:Alq3に、緑発光ドーパント:coumarin6(クマリン6、λmax=510nm)を2%ドープしたものである。また、膜厚については、表1に示すとおりである。
以下に、実施例16のデバイス構造(層構成)と各層の膜厚を示す。
基板5 : ガラス基板(0.7mm)
陽極4b : ITO (150nm)
正孔注入層31 : CuPc (30nm)
正孔輸送層32 : TPD (30nm)
リン光赤色発光層12: CBP:btp2Ir(acac) (30nm)
リン光緑色発光層11: CBP:Ir(ppy)3 (10nm)
電子輸送層33 : BCP (30nm)
中間層3(第1層) : BCP:Li (10nm)
中間層3(第2層) : ITO (10nm)
正孔輸送層34 : TPD (30nm)
蛍光青色発光層22 : TBADN:TBP:NPD (20nm)
蛍光緑色発光層21 : Alq3:C545T (15nm)
電子輸送層35 : BCP (20nm)
電子注入層36 : LiF (1nm)
陰極4a : Al (80nm)
なお、実施例16の有機電界発光素子は、実施例4の有機電界発光素子について、リン光ユニット1と蛍光ユニット2とを入れ替えた構成となっている。これにより、積層順の違いによる素子特性を評価することができる。
(発光スペクトル)
各有機電界発光素子の発光スペクトルを、分光放射輝度計(コニカミノルタ製CS-2000)を用いて測定した。
各有機電界発光素子を電源(KEYTHLEY2400)に接続し、電流密度10mA/cm2の定電流を通電し、積分球(ラブスフェア社製SLMS-CDS)を用いて電力効率を測定した。
各有機電界発光素子を電源(KEYTHLEY2400)に接続し、電流密度10mA/cm2の定電流を通電し、連続発光させたときの輝度を輝度計(コニカミノルタ製LS-110)を用いて観測し、輝度が半減する半減時間を測定した。また同時に、発光色度の変化について観測し、初期の発光色度と比較して色度変化量が0.01以上となる変色時間を測定した。輝度が半減する時間(半減時間)と、色度変化量が0.01以上となる時間(変色時間)のうち、短いほうの時間を素子の寿命とした。
図2に、実施例1~5の有機電界発光素子の発光スペクトルを示す。また、図3に、比較例1~5の有機電界発光素子の発光スペクトルを示す。なお、各発光スペクトルは、赤色波長領域での最大発光強度を「1」として規格化したものである。
の最大発光強度(IG)と、青色波長領域での最大発光強度(IB)との相対強度を示す。ここで、各色の最大発光強度を示す波長は、次の通りである。
緑:λ(green):525nm
赤:λ(red) :620nm
表3に示すように、実施例1~5で得られる発光スペクトルの強度は、赤が最も強く、緑、青の順になっている。なお、表3中の波長は、各実施例における、赤色波長領域での最大発光強度(IR)を1としたときの相対値である。
基板5 : ガラス基板(0.7mm)
陽極4b : ITO (150nm)
正孔注入層31 : CuPc (30nm)
正孔輸送層32 : TPD (30nm)
蛍光青色発光層22 : TBADN:TBP:NPD (Xnm)
蛍光緑色発光層21 : Alq3:C545T (Ynm)
電子輸送層33 : BCP (30nm)
電子注入層36 : LiF (1nm)
陰極4a : Al (80nm)
<リン光ユニット評価素子:評価素子6~10>
基板5 : ガラス基板(0.7mm)
陽極4b : ITO (150nm)
正孔注入層31 : CuPc (30nm)
正孔輸送層34 : TPD (30nm)
リン光赤色発光層12: CBP:btp2Ir(acac) (αnm)
リン光緑色発光層11: CBP:Ir(ppy)3 (βnm)
電子輸送層35 : BCP (20nm)
電子注入層36 : LiF (1nm)
陰極4a : Al (80nm)
なお、各評価素子の膜厚については、表5に示すとおりである。すなわち、評価素子1~5、及び評価素子6~10の膜厚が、それぞれ実施例1~5の膜厚に対応している。
Ir(ppy)3:λmax=520nm (リン光緑色発光層11)
C545T:λmax=525nm (蛍光緑色発光層21)
rubrene:λmax=560nm (蛍光緑色発光層21)
すなわち、リン光緑色発光層11の発光ドーパントの波長と蛍光緑色発光層21の発光ドーパントの波長との波長差は、実施例1~5では5nm、実施例6~10では40nmとなっている。この波長差は、リン光ユニット1における最大発光強度を示す緑色発光波長(λGT)と、蛍光ユニット2における最大発光強度を示す緑色発光波長(λGS)との波長差に等しいといえる。すなわち、実施例1~5では、λGS-λGT=5<10の関係になっている。
Claims (18)
- リン光赤色発光層と、リン光緑色発光層と、蛍光青色発光層と、蛍光緑色発光層とを備えてなることを特徴とする有機電界発光素子。
- 上記リン光赤色発光層と上記リン光緑色発光層とを含むリン光ユニットと、上記蛍光青色発光層と上記蛍光緑色発光層とを含む蛍光ユニットとを備え、上記リン光ユニットと上記蛍光ユニットとが中間層を介して接続されていることを特徴とする請求項1に記載の有機電界発光素子。
- 陽極と、陰極と、上記リン光赤色発光層と上記リン光緑色発光層とを含むリン光ユニットと、上記蛍光青色発光層と上記蛍光緑色発光層とを含む蛍光ユニットとを備え、上記リン光ユニットが上記蛍光ユニットよりも上記陰極側に配置されていることを特徴とする請求項1に記載の有機電界発光素子。
- 陽極と、陰極と、上記リン光ユニットと、上記蛍光ユニットとを備え、上記リン光ユニットが上記蛍光ユニットよりも上記陰極側に配置されていることを特徴とする請求項2に記載の有機電界発光素子。
- 上記リン光赤色発光層と上記リン光緑色発光層とを含むリン光ユニットと、上記蛍光青色発光層と上記蛍光緑色発光層とを含む蛍光ユニットとを備え、上記リン光ユニットにおける、赤色発光波長(λRT)の最大強度[I(λRT)]と緑色発光波長(λGT)の最大強度[I(λGT)]との比[I(λGT)/I(λRT)]が、I(λGT)/I(λRT)<0.65を満たし、上記蛍光ユニットにおける、青色発光波長(λBS)の最大強度[I(λBS)]と緑色発光波長(λGS)の最大強度[I(λGS)]との比[I(λGS)/I(λBS)]が、I(λGS)/I(λBS)>0.3を満たすことを特徴とする請求項1に記載の有機電界発光素子。
- 上記リン光ユニットと、上記蛍光ユニットとを備え、上記リン光ユニットにおける、赤色発光波長(λRT)の最大強度[I(λRT)]と緑色発光波長(λGT)の最大強度[I(λGT)]との比[I(λGT)/I(λRT)]が、I(λGT)/I(λRT)<0.65を満たし、上記蛍光ユニットにおける、青色発光波長(λBS)の最大強度[I(λBS)]と緑色発光波長(λGS)の最大強度[I(λGS)]との比[I(λGS)/I(λBS)]が、I(λGS)/I(λBS)>0.3を満たすことを特徴とする請求項2~4のいずれか1項に記載の有機電界発光素子。
- 上記リン光赤色発光層と上記リン光緑色発光層とを含むリン光ユニットと、上記蛍光青色発光層と上記蛍光緑色発光層とを含む蛍光ユニットとを備え、上記リン光ユニットにおける緑色発光波長(λGT)と、上記蛍光ユニットにおける緑色発光波長(λGS)との波長差が、絶対値で10nm以下であることを特徴とする請求項1に記載の有機電界発光素子。
- 上記リン光ユニットと、上記蛍光ユニットとを備え、上記リン光ユニットにおける緑色発光波長(λGT)と、上記蛍光ユニットにおける緑色発光波長(λGS)との波長差が、絶対値で10nm以下であることを特徴とする請求項2~6のいずれか1項に記載の有機電界発光素子。
- 上記蛍光青色発光層の発光ドーパントのイオン化ポテンシャル(IpB)は上記蛍光緑色発光層の発光ドーパントのイオン化ポテンシャル(IpG)よりも大きく、上記蛍光青色発光層の発光ドーパントの電子親和力(EaB)は上記蛍光緑色発光層の発光ドーパントの電子親和力(EaG)よりも大きいことを特徴とする請求項1~8のいずれか1項に記載の有機電界発光素子。
- 上記リン光赤色発光層と、上記リン光緑色発光層と、上記蛍光青色発光層と、上記蛍光緑色発光層における発光色の混色が、W色、WW色、L色のいずれかであることを特徴とする請求項1~9のいずれか1項に記載の有機電界発光素子。
- 赤色波長領域での最大強度(IR)と、緑色波長領域での最大強度(IG)と、青色波長領域での最大強度(IB)とが、この順で弱くなる(IR>IG>IB)ことを特徴とする請求項1~10のいずれか1項に記載の有機電界発光素子。
- 請求項1~11に記載の有機電界発光素子において、上記リン光赤色発光層は、赤色のりん光を発するりん光赤色の発光ドーパントを含み、上記りん光赤色の発光ドーパントは、ビス-(3-(2-(2-ピリジル)ベンゾチエニル)モノ-アセチルアセトネート)イリジウム(III))、ビス‐(2‐フェニルベンゾチアゾレート)(アセチルアセトナート)イリジウム(Bis(2-phenylbenzothiazolato)(acetylacetonate)iridium(III))、2,3,7,8,12,13,17,18-オクタエチル‐21H,23H‐ポルフィリン白金(2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin platinum(II))からなる群より選択される一つの物質から形成される。
- 請求項1~12に記載の有機電界発光素子において、上記リン光緑色発光層は、緑色のりん光を発するりん光緑色の発光ドーパントを含み、上記りん光緑色の発光ドーパントは、ファクトリス(2-フェニルピリジン)イリジウム、ビス‐(2フェニルピリジン)(アセチルアセトナート)イリジウム(Bis(2-phenylpyridine)(acetylacetonate)iridium(III))、トリス[2‐(パラ‐トリル)ピリジン]イリジウム(Tris[2-(p-tolyl)pyridine]iridium(III))からなる群より選択される一つの物質から形成される。
- 請求項1~13に記載の有機電界発光素子において、上記蛍光青色発光層は、青色の蛍光を発する蛍光青色の発光ドーパントを含み、上記蛍光青色の発光ドーパントは、1-tert-ブチル-ペリレン(TBP)、4,4'‐ビス(9‐エチル‐3‐カルバゾビニレン)‐1,1’‐ビフェニル(4,4'-Bis(9-ethyl-3-carbazovinylene)-1,1'-biphenyl)、ペリレンからなる群より選択される一つの物質から形成される。
- 請求項14に記載の有機電界発光素子において、上記蛍光青色発光層は、電荷移動補助ドーパントをさらに含み、上記電荷移動補助ドーパントは、4,4’-ビス[N-(ナフチル)-N-フェニル-アミノ]ビフェニル、N,N’-ビス(3-メチルフェニル)-N,N’-ビス(ビフェニル)-ベンジダイン(N, N'-Bis(3-methylphenyl)-N,N'-bis(phenyl)-benzidine)、N,N’-ビス(3メチルフェニル)-N,N’-ビス(ビフェニル)-9,9-スピロビフルオレン(N, N'-Bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-spirobifluorene)からなる群より選択される一つの物質から形成される。
- 請求項1~15に記載の有機電界発光素子において、上記蛍光緑色発光層は、緑色の蛍光を発する蛍光緑色の発光ドーパントを含み、上記蛍光緑色の発光ドーパントは、2,3,6,7‐テトラヒドロ-1,1,7,7,-テトラメチル-1H,5H,11H-10(2-ベンゾチアゾリル)キノリジノ-[9,9a,1gh]クマリン(2,3,6,7-Tetrahydro-1,1,7,7,-tetramethyl-1H,5H,11H-10-(2-benzothiazolyl)quinolizino-[9,9a,1gh]coumarin)、N,N’-ジメチル-キナクリドン(N,N'-Dimethyl-quinacridone)、クマリン6、ルブレンからなる群より選択される一つの物質から形成される。
- 請求項16に記載の有機電界発光素子において、上記蛍光緑色の発光ドーパントを取り込むホストは、トリス(8-オキソキノリン)アルミニウム(III)、9,10-ジ-(2-ナフチル)アントラセン(9,10-Di-(2naphthyl)anthracene)、ビス(9,9’-ジアリールフルオレン)(bis(9,9'-diarylfluorene))からなる群より選択される一つの物質から形成される。
- 請求項16または17に記載の有機電界発光素子において、上記蛍光緑色の発光ドーパントのドープ濃度は1~20質量%である。
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US20120248424A1 (en) | 2012-10-04 |
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CN102668707A (zh) | 2012-09-12 |
CN102668707B (zh) | 2015-02-18 |
KR101417789B1 (ko) | 2014-08-06 |
KR20120088714A (ko) | 2012-08-08 |
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