WO2013171872A1 - Panneau électroluminescent (el) organique et dispositif électroluminescent - Google Patents

Panneau électroluminescent (el) organique et dispositif électroluminescent Download PDF

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Publication number
WO2013171872A1
WO2013171872A1 PCT/JP2012/062596 JP2012062596W WO2013171872A1 WO 2013171872 A1 WO2013171872 A1 WO 2013171872A1 JP 2012062596 W JP2012062596 W JP 2012062596W WO 2013171872 A1 WO2013171872 A1 WO 2013171872A1
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Prior art keywords
organic
light emitting
transport layer
light
emitting panel
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PCT/JP2012/062596
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English (en)
Japanese (ja)
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大志 辻
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パイオニア株式会社
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Priority to PCT/JP2012/062596 priority Critical patent/WO2013171872A1/fr
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/155—Hole transporting layers comprising dopants
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • 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
    • H10K2101/10—Triplet emission
    • 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
    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Definitions

  • the present invention relates to an organic EL (Electro Luminescence) light emitting panel and a light emitting device using the same.
  • a light emitting device using an organic EL light emitting panel having an organic EL element as a light emitting source has been proposed.
  • a light emitting device using an organic EL light emitting panel has a feature that there is no restriction in shape due to surface light emission, and such a feature cannot be obtained by other light emitting devices such as an LED (light emitting diode) light emitting device. Further development for the practical use of is expected.
  • the organic EL element In the organic EL light emitting panel, the organic EL element generates heat during light emission, although not as much as the LED. This heat generation changes the organic layer carrier mobility and carrier injection in the organic EL element. This causes a change in the balance between the amount of electrons injected into the light emitting layer and the amount of holes injected into the light emitting layer in the organic EL element. As a result, the current efficiency changes until the panel temperature is stabilized. Therefore, even if a constant current is supplied, the organic EL light emitting panel has a characteristic that the light emission luminance changes from the start of current supply until the panel temperature is stabilized. In particular, there is a drawback in that the light emission luminance is low at the beginning of lighting from the start of current supply until the panel temperature is stabilized, and the user feels dark.
  • Patent Document 1 discloses that a temperature of an organic EL panel is detected by a temperature sensor, and the desired temperature is determined regardless of the temperature based on the detected panel temperature. An apparatus for supplying electric energy to an organic EL panel so that the amount of emitted light can be obtained is shown.
  • Japanese Patent Application Laid-Open No. 2004-26883 discloses an illumination device including an organic EL element and a control circuit unit, the control circuit unit having a luminance adjustment circuit, and the luminance adjustment circuit is organic in accordance with a signal from a temperature sensor that detects the ambient temperature.
  • a configuration having a function of controlling the luminance of the EL element is shown.
  • a temperature change deterioration correction table is stored so that the light emitting element of the surface light source unit has a preset brightness, and the temperature change deterioration correction is performed on a signal indicating the ambient temperature detected by the temperature sensor.
  • Data is output and a voltage corresponding to the deterioration correction data is applied to the organic EL element.
  • Patent Document 3 a panel temperature detection signal from a panel temperature sensor that detects the panel temperature of the organic EL panel is supplied to the control unit, and the control unit uses the panel temperature detection signal from the panel temperature sensor to perform organic processing.
  • An apparatus configured to perform temperature compensation control of an EL panel is shown.
  • Patent Documents 1 to 3 in a conventional light emitting device including a temperature sensor that detects the temperature of an organic EL light emitting panel, a voltage supplied to the organic EL light emitting panel according to a detection temperature of the temperature sensor or Since the current is controlled, the light emission luminance of the organic EL light emitting panel can be stabilized to a desired luminance during the period from the start of current supply to the organic EL light emitting panel until the panel temperature is stabilized.
  • a temperature sensor in this way increases the cost of the light emitting device.
  • the problem to be solved by the present invention includes the above-mentioned drawbacks as an example, and an organic EL light-emitting panel having a simple configuration capable of avoiding a reduction in light emission luminance at the beginning of lighting and a low-cost organic EL light-emitting panel. It is an object of the present invention to provide a light emitting device.
  • An organic EL light-emitting panel includes a substrate, a transparent electrode formed on the substrate, an organic functional layer formed on the transparent electrode, and a metal formed on the organic functional layer.
  • An organic EL light-emitting panel comprising an electrode, wherein the organic functional layer includes a hole transport layer, an electron transport layer, and a light-emitting layer sandwiched between the hole transport layer and the electron transport layer,
  • a light-emitting device is a light-emitting device including an organic EL light-emitting panel and a current control unit that supplies a constant driving current to the organic EL light-emitting panel in a current supply mode, the organic EL light-emitting device.
  • the panel comprises a substrate, a transparent electrode formed on the substrate, an organic functional layer formed on the transparent electrode, and a metal electrode formed on the organic functional layer, and the transparent electrode
  • the drive current is supplied between the metal electrodes, and the organic functional layer includes a hole transport layer, an electron transport layer, and a light emitting layer sandwiched between the hole transport layer and the electron transport layer.
  • the organic EL light emitting panel has a quantitative imbalance between the amount of holes injected into the light emitting layer by the hole transport layer and the amount of electrons injected into the light emitting layer by the electron transport layer in the current supply mode. in front It is characterized by having a larger characteristic with increasing temperature of the organic EL light emitting panel.
  • the organic EL light-emitting panel of the invention according to claim 1 and the light-emitting device of the invention according to claim 7, includes an injection amount of holes into the light-emitting layer by the hole transport layer and a light-emitting layer by the electron transport layer.
  • the relative change with the amount of electrons injected into the organic EL panel increases as the temperature of the organic EL light-emitting panel increases.
  • the emission luminance gradually decreases as the temperature increases. Therefore, by setting the light emission luminance of the organic EL light emitting panel to a desired luminance when the panel temperature is stabilized, a light emission luminance equal to or higher than the desired luminance can be obtained immediately at the beginning of lighting. In addition, it is possible to eliminate the fact that the luminance is felt dark by the user at low cost.
  • FIG. 1 shows a configuration of a light-emitting device that is Embodiment 1 of the present invention.
  • the light emitting device includes a power supply unit 11, an AC-DC converter 12, a current control unit 13, an organic EL light emitting panel 14, and an operation unit 15.
  • the power supply unit 11 is, for example, a commercial power supply input unit.
  • the output voltage of the AC-DC converter 12 is supplied to the current control unit 13 as a DC power source.
  • the operation unit 15 instructs the current control unit 13 alternately as a current supply mode and a current supply stop mode for each user operation.
  • the current control unit 13 is composed of, for example, a circuit using a drive transistor, and supplies the direct current supplied from the AC-DC converter 12 to the organic EL light emitting panel 14 as a drive current in the current supply mode.
  • the drive current is a constant current.
  • the organic EL light-emitting panel 14 is a white light-emitting panel having a light-emitting area of 100 mm ⁇ 100 mm.
  • the anode 22, the hole injection layer 23, the hole transport layer 24, and the red-green light-emitting layer 25 are formed on the glass substrate 21.
  • a blue light emitting layer 26, an electron transport layer 27, and a cathode 28 are stacked in that order.
  • the hole injection layer 23, the hole transport layer 24, the red-green light emitting layer 25, the blue light emitting layer 26, and the electron transport layer 27 are organic functional layers.
  • the anode 22 is a transparent electrode and is made of, for example, an ITO film having a thickness of 120 nm by sputtering.
  • the hole injection layer 23 to the cathode 28 are formed by resistance heating vapor deposition.
  • the hole injection layer 23 is made of MoO 3 and has a thickness of 5 nm.
  • the hole transport layer 24 is made of NPB of an aryl (aromatic ring) amine compound, and has a thickness of 30 nm.
  • the red-green light emitting layer 25 has a thickness of 30 nm, and 26DCzPPy is used as a host material, and Ir (2-phq) 2 acac Is added as a red dopant in 2% volume addition, and Ir (ppy) 3 is added as a green dopant in 9% volume addition.
  • the blue light-emitting layer 26 has a thickness of 15 nm, and has PAND as a host material and DPAVBi as a dopant with a 5% volume addition.
  • the electron transport layer 27 has a thickness of 25 nm, is made of NBphen which is a heteroaromatic ring compound, and has 10% volume addition of CsxMoOy as a donor dopant.
  • the cathode 28 is a metal electrode and is made of an Al film having a thickness of 100 nm.
  • 26DCzPPy has a structure as shown in the following chemical formula
  • Ir (2-phq) 2 acac has a structure represented by the following chemical formula.
  • the internal structure of the organic EL light-emitting panel 14 is an example, and the present invention is not limited to this.
  • the drive current supplied from the current control unit 13 flows in the organic EL light emitting panel 14 from the anode 22 to the cathode 30 of the organic EL light emitting panel 14.
  • FIG. 3 shows a result of actually measuring changes in luminance and panel temperature with respect to an elapsed time from the start time when a current density of 20 mA / cm 2 is supplied to the organic EL light-emitting panel 14 as a constant current from the start time of the current supply mode. It is shown as a table. The luminance decreases over a period until the panel temperature is saturated. In the measurement of FIG. 3, it was confirmed that the panel temperature reached thermal equilibrium after the lapse of 15 minutes, and the decrease in brightness and the increase in panel temperature were saturated. The luminance was stable at approximately 2000 cd / m 2 .
  • the inventor of the present invention shows the temperature dependence of the current-voltage characteristics of the hole transport layer material and the electron transport layer material as follows. Made and confirmed by it.
  • ITO having a film thickness of 120 nm is formed on the glass substrate 41 as the anode 42, and the hole injection layer 43 is formed on the anode 42.
  • MoO 3 is deposited in a thickness of 5 nm
  • NPB is deposited by resistance heating deposition in a thickness of 150nm as a hole transport layer 44 thereon as.
  • Au is formed as a cathode 45 on the hole transport layer 44 by resistance heating vapor deposition with a film thickness of 100 nm.
  • Al is formed on the glass substrate 51 as an anode 52 by a resistance heating vapor deposition with a film thickness of 120 nm.
  • NBphen and CsxMoOx are formed as an electron transport layer 53 by co-evaporation with a film thickness of 150 nm.
  • the mixing ratio at this time is 9: 1 by volume ratio.
  • Al is formed as a cathode 54 on the electron transport layer 53 by resistance heating vapor deposition with a film thickness of 100 nm.
  • Al is formed on the glass substrate 61 as the anode 62 by resistance heating vapor deposition with a film thickness of 120 nm. ing.
  • Alq 3 is deposited as an electron transport layer 63 with a film thickness of 150 nm.
  • Li 2 O is formed with a thickness of 1 nm as an electron injection layer 64, and further, Al is formed thereon with a thickness of 100 nm by resistance heating vapor deposition as a cathode 65.
  • the current characteristics of the Hall single charge device 40 and the electronic single charge devices 50 and 60 with respect to a constant applied voltage (7 V) were measured at respective device temperatures of 23 ° C., 35 ° C., and 50 ° C.
  • the measurement results are as shown in FIG.
  • the current values are almost the same at the element temperature of 23 ° C., which is approximately room temperature, but the element temperature rises. Accordingly, it was confirmed that the rate of increase of the current value of the Hall single charge device 40 was larger than that of the electronic single charge device 50.
  • the current value increase rate of the Hall single charge device 40 is 1.68
  • the current value increase rate of the electronic single charge device 50 is 1.19.
  • the carrier temperature bias (quantitative imbalance) is caused by the panel temperature. It gets bigger as you go up. That is, the quantitative imbalance between the amount of holes injected into the light emitting layer 25 by the hole transport layer 24 and the amount of electrons injected into the light emitting layer 26 by the electron transport layer 27 increases as the panel temperature increases.
  • the current value of the hole single charge element 40 at the element temperature of 23 ° C. is sufficiently larger than the current value of the electronic single charge element 60, but the element temperature increases. As a result, it was confirmed that the rate of increase of the current value of the electronic single charge device 60 was larger than that of the Hall single charge device 40.
  • the organic EL light emitting panel 80 using Alq 3 is a white light emitting panel having a light emitting area of 100 mm ⁇ 100 mm, and Alq 3 having a thickness of 25 nm is formed as the electron transport layer 81, and the electron injection layer 82. As a result, Li 2 O having a thickness of 1 nm is formed.
  • Other structures are the same as those of the organic EL light-emitting panel 14 shown in FIG.
  • FIG. 9 shows a result of actually measuring changes in luminance and panel temperature with respect to an elapsed time from the start time when a current density of 15 mA / cm 2 was supplied to the organic EL light emitting panel 80 as a constant current from the start time of the current supply mode. It is shown as a table. As can be seen from FIG. 9, the light emission luminance of the organic EL light emitting panel 80 increases over a period until the panel temperature is saturated. In the measurement result of FIG. 9, it was confirmed that the panel temperature reached thermal equilibrium after the elapse of 15 minutes, and the increase in light emission luminance was saturated as the panel temperature increased.
  • the organic EL light emitting panel 80 using NPB as the material of the hole transport layer 24 and Alq 3 as the material of the electron transport layer 81, holes to the light emitting layer 25 by the hole transport layer 24 due to an increase in the panel temperature. It can be seen that the rate of increase in the amount of injected hydrogen is smaller than the rate of increase in the amount of injected electron into the light emitting layer 26 by the electron transport layer 81. That is, in the organic EL light emitting panel 80, the carrier balance deviation (quantitative imbalance) becomes smaller as the panel temperature increases.
  • the organic EL light-emitting panel 14 when a constant drive current is passed from the current control unit 13 to the organic EL light-emitting panel 14 in the current supply mode as described above, the organic EL light-emitting panel 14 is The panel temperature gradually rises according to the elapsed time, while the luminance has a characteristic including a gradually decreasing portion and a flat portion following the gradually decreasing portion as shown in FIG. Therefore, by setting the light emission luminance of the organic EL light-emitting panel 14 to a desired luminance when the panel temperature reaches thermal equilibrium, the luminance higher than the desired luminance is obtained at the beginning of lighting when the current supply mode is started. Because it is obtained, it feels bright to the user. As a result, an organic EL light-emitting panel that can avoid a reduction in light emission luminance at the beginning of lighting and a light-emitting device using the same can be realized with a simple configuration and at low cost.
  • the light emitting device of the present invention is used for illumination, stable illumination can be provided to the user immediately after the start of lighting.
  • an organic EL light emitting panel using NPB as the material for the hole transport layer and NBphen and CsxMoOx as the material for the electron transport layer is shown. If the difference between the injection amount of electrons and the amount of electrons injected into the light emitting layer by the electron transport layer increases as the temperature of the organic EL light emitting panel rises, and the characteristic that the emission luminance gradually decreases as the temperature rises can be obtained.
  • the present invention does not limit the materials of the hole transport layer and the electron transport layer.
  • Aromatic aromatic amine compounds can be used for the hole transport layer, and heteroaromatic ring compounds having a skeleton such as pyridine, triazine, 1,10-phenanthroline, phenoxazine, and phenazine for the electron transport layer.
  • the donor dopant may be any dopant that forms a charge transfer complex with the heteroaromatic ring compound contained in the electron transport layer.
  • the transparent electrode serves as the anode and the metal electrode serves as the cathode.
  • the present invention is not limited to this, and the metal electrode serves as the anode and the transparent electrode serves as the cathode. Even if the layer is formed, the same effect as the above-described embodiment can be obtained.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention se rapporte à un panneau électroluminescent (EL) organique qui comprend : un substrat ; des électrodes transparentes formées sur le substrat ; une couche fonctionnelle organique formée sur les électrodes transparentes ; et des électrodes métalliques formées sur la couche fonctionnelle organique ; et qui présente la caractéristique selon laquelle le déséquilibre quantitatif du niveau d'injection de trous dans la couche électroluminescente par la couche de transport de trous et du niveau d'injection d'électrons dans la couche électroluminescente par la couche de transport d'électrons est progressivement plus important à mesure que la température du panneau électroluminescent (EL) augmente. L'invention se rapporte également à un dispositif électroluminescent qui comprend le panneau électroluminescent (EL).
PCT/JP2012/062596 2012-05-17 2012-05-17 Panneau électroluminescent (el) organique et dispositif électroluminescent WO2013171872A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10547019B2 (en) 2014-10-09 2020-01-28 Nippon Chemical Industrial Co., Ltd. Electrochemical luminescent cell and composition for forming luminescent layer of electrochemical luminescent cell

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003083009A1 (fr) * 2002-03-29 2003-10-09 Pioneer Corporation Element electroluminescent organique
JP2003323988A (ja) * 2002-02-28 2003-11-14 Semiconductor Energy Lab Co Ltd 発光装置及びそれを用いた電気器具
WO2009110075A1 (fr) * 2008-03-05 2009-09-11 パイオニア株式会社 Elément à semi-conducteurs organique
WO2010016101A1 (fr) * 2008-08-04 2010-02-11 パイオニア株式会社 Élément électroluminescent organique
WO2012023177A1 (fr) * 2010-08-17 2012-02-23 パイオニア株式会社 Élément électroluminescent organique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003323988A (ja) * 2002-02-28 2003-11-14 Semiconductor Energy Lab Co Ltd 発光装置及びそれを用いた電気器具
WO2003083009A1 (fr) * 2002-03-29 2003-10-09 Pioneer Corporation Element electroluminescent organique
WO2009110075A1 (fr) * 2008-03-05 2009-09-11 パイオニア株式会社 Elément à semi-conducteurs organique
WO2010016101A1 (fr) * 2008-08-04 2010-02-11 パイオニア株式会社 Élément électroluminescent organique
WO2012023177A1 (fr) * 2010-08-17 2012-02-23 パイオニア株式会社 Élément électroluminescent organique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10547019B2 (en) 2014-10-09 2020-01-28 Nippon Chemical Industrial Co., Ltd. Electrochemical luminescent cell and composition for forming luminescent layer of electrochemical luminescent cell

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