WO2020240330A1 - 発光デバイス、発光装置、発光モジュール、電子機器、及び照明装置 - Google Patents
発光デバイス、発光装置、発光モジュール、電子機器、及び照明装置 Download PDFInfo
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- WO2020240330A1 WO2020240330A1 PCT/IB2020/054664 IB2020054664W WO2020240330A1 WO 2020240330 A1 WO2020240330 A1 WO 2020240330A1 IB 2020054664 W IB2020054664 W IB 2020054664W WO 2020240330 A1 WO2020240330 A1 WO 2020240330A1
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- light emitting
- organic compound
- emitting device
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- layer
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- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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Definitions
- One aspect of the present invention relates to a light emitting device, a light emitting device, a light emitting module, an electronic device, and a lighting device.
- One aspect of the present invention is not limited to the above technical fields.
- the technical fields of one aspect of the present invention include semiconductor devices, display devices, light emitting devices, power storage devices, storage devices, electronic devices, lighting devices, input devices (for example, touch sensors), input / output devices (for example, touch panels, etc.). ), Their driving method, or their manufacturing method can be given as an example.
- organic EL devices also referred to as organic EL devices and organic EL elements
- EL organic electroluminescence
- the basic configuration of an organic EL device is such that a layer containing a luminescent organic compound (hereinafter, also referred to as a light emitting layer) is sandwiched between a pair of electrodes. By applying a voltage to this organic EL device, light emission from a luminescent organic compound can be obtained.
- a luminescent organic compound hereinafter, also referred to as a light emitting layer
- Examples of the luminescent organic compound include a compound capable of converting a triplet excited state into luminescence (also referred to as a phosphorescent compound or a phosphorescent material).
- Patent Document 1 discloses an organometallic complex having iridium or the like as a central metal as a phosphorescent material.
- image sensors are used in various applications such as personal authentication, defect analysis, medical diagnosis, and security-related applications.
- the wavelength of the light source used for the image sensor is properly used according to the application.
- light having various wavelengths such as visible light, short wavelength light such as X-ray, and long wavelength light such as near infrared light is used.
- light emitting devices are also being studied for application as light sources for image sensors as described above.
- One of the problems in one aspect of the present invention is to provide a light emitting device that emits near-infrared light and in which visible light is hard to be visually recognized.
- One of the problems in one aspect of the present invention is to increase the luminous efficiency of a light emitting device that emits near infrared light.
- One of the problems in one aspect of the present invention is to improve the reliability of a light emitting device that emits near-infrared light.
- One aspect of the present invention has a light emitting organic compound and a host material in the light emitting layer, the maximum peak wavelength of the light emitting spectrum is 750 nm or more and 900 nm or less, and the brightness A [cd / m 2 ] and the radiance B.
- [W / sr / m 2 ] is a light emitting device that satisfies 0 ⁇ A / B ⁇ 1 [cd ⁇ sr / W].
- One aspect of the present invention has a light emitting organic compound and a host material in the light emitting layer, the maximum peak wavelength of the light emitting spectrum is 750 nm or more and 900 nm or less, and the brightness A [cd / m 2 ] and the radiance B.
- [W / sr / m 2 ] is a light emitting device that satisfies 0 ⁇ A / B ⁇ 1 [cd ⁇ sr / W].
- the difference between the HOMO level and the LUMO level in the host material is preferably 1.35 eV or more and 2.25 eV or less.
- the host material preferably has a first organic compound and a second organic compound.
- the HOMO level of the first organic compound is preferably higher than the HOMO level of the second organic compound.
- the difference between the HOMO level of the first organic compound and the LUMO level of the second organic compound is preferably smaller than the difference between the HOMO level and the LUMO level of the luminescent organic compound.
- the first organic compound and the second organic compound are preferably substances that form an excited complex.
- the difference between the HOMO level of the first organic compound and the LUMO level of the second organic compound is preferably 1.35 eV or more and 2.25 eV or less.
- One aspect of the present invention has a luminescent organic compound and a host material in the light emitting layer, the maximum peak wavelength of the luminescence spectrum is 750 nm or more and 900 nm or less, and the HOMO level of the host material is the luminescent organic compound.
- the difference between the HOMO level and the LUMO level of the host material is smaller than the difference between the HOMO level and the LUMO level of the luminescent organic compound, which is 0.4 eV or more higher than the HOMO level of the light emitting device. Is.
- the difference between the HOMO level and the LUMO level in the host material is preferably 1.35 eV or more and 2.25 eV or less.
- One aspect of the present invention has a luminescent organic compound and a host material in the light emitting layer, the maximum peak wavelength of the emission spectrum is 750 nm or more and 900 nm or less, and the host material is the first organic compound and the second organic compound.
- the HOMO level of the first organic compound is 0.4 eV or more higher than the HOMO level of the luminescent organic compound
- the HOMO level of the first organic compound is the second organic compound.
- the difference between the HOMO level of the first organic compound and the LUMO level of the second organic compound is higher than the difference between the HOMO level and the LUMO level of the luminescent organic compound. It is a small, light emitting device.
- the first organic compound and the second organic compound are preferably substances that form an excited complex.
- the difference between the HOMO level of the first organic compound and the LUMO level of the second organic compound is preferably 1.35 eV or more and 2.25 eV or less.
- the rising wavelength of the maximum peak on the short wavelength side in the emission spectrum is preferably 650 nm or more.
- the luminescent organic compound preferably has a rising wavelength of 650 nm or more on the short wavelength side of the maximum peak of the PL spectrum in the solution.
- the external quantum efficiency of the light emitting device is preferably 1% or more.
- the luminescent organic compound is preferably an organometallic complex having a metal-carbon bond.
- the organometallic complex preferably has a condensed complex aromatic ring having 2 or more and 5 or less rings.
- the fused complex aromatic ring is preferably coordinated to a metal.
- the luminescent organic compound is preferably a cyclometal complex.
- the luminescent organic compound is preferably an orthometal complex.
- the luminescent organic compound is preferably an iridium complex.
- One aspect of the present invention is a light emitting device having a light emitting device having any of the above configurations and one or both of a transistor and a substrate.
- One aspect of the present invention is a module having the above light emitting device and attached with a connector such as a flexible printed circuit board (hereinafter referred to as FPC) or TCP (Tape Carrier Package), or a COG (Chip).
- a connector such as a flexible printed circuit board (hereinafter referred to as FPC) or TCP (Tape Carrier Package), or a COG (Chip).
- FPC flexible printed circuit board
- TCP Tape Carrier Package
- COG Chip
- It is a light emitting module such as a light emitting module in which an integrated circuit (IC) is mounted by an On Glass method or a COF (Chip On Film) method.
- the light emitting module of one aspect of the present invention may have only one of the connector and the IC, or may have both.
- One aspect of the present invention is an electronic device having the above-mentioned light emitting module and at least one of an antenna, a battery, a housing, a camera, a speaker, a microphone, and an operation button.
- One aspect of the present invention is a lighting device having the above-mentioned light emitting device and at least one of a housing, a cover, and a support base.
- the present invention it is possible to provide a light emitting device that emits near infrared light and in which visible light is hard to be visually recognized.
- the luminous efficiency of a light emitting device that emits near infrared light can be increased.
- the reliability of a light emitting device that emits near infrared light can be enhanced.
- FIG. 1A to 1C are diagrams showing an example of a light emitting device.
- FIG. 2A is a top view showing an example of the light emitting device.
- 2B and 2C are cross-sectional views showing an example of a light emitting device.
- FIG. 3A is a top view showing an example of the light emitting device.
- FIG. 3B is a cross-sectional view showing an example of a light emitting device.
- 4A to 4E are diagrams showing an example of an electronic device.
- FIG. 5 is a cross-sectional view showing a light emitting device of the embodiment.
- FIG. 6 is a diagram showing an emission spectrum of the light emitting device of the example.
- FIG. 7 is a diagram showing an emission spectrum of the light emitting device of the example.
- FIG. 8 is a diagram showing emission spectra of the light emitting device and the mixed film of the example.
- FIG. 9 is a diagram showing emission spectra of the light emitting device and the mixed film of the example.
- FIG. 10 is a diagram showing emission spectra of the light emitting device and the mixed film of the example.
- FIG. 11 is a diagram showing emission spectra of the light emitting device and the mixed film of the example.
- FIG. 12 is a diagram showing an absorption spectrum of [Ir (dmdppbq) 2 (dpm)].
- FIG. 13 is a diagram showing an emission spectrum of [Ir (dmdppbq) 2 (dpm)].
- membrane and the word “layer” can be interchanged with each other in some cases or depending on the situation.
- conductive layer can be changed to the term “conductive layer”.
- insulating film can be changed to the term “insulating layer”.
- the light emitting device of one aspect of the present invention has a light emitting organic compound (also referred to as a guest material) and a host material in the light emitting layer.
- a light emitting organic compound also referred to as a guest material
- a host material in the light emitting layer.
- the maximum peak wavelength (wavelength having the highest peak intensity) of the light emitting spectrum is 750 nm or more and 900 nm or less, preferably 780 nm or more, and also. , 880 nm or less is preferable.
- the brightness A [cd / m 2 ] and the radiance B [W / sr / m 2 ] satisfy 0 ⁇ A / B ⁇ 1 [cd ⁇ sr / W]. Is preferable. Alternatively, it is preferable that the brightness A [cd / m 2 ] and the radiance B [W / sr / m 2 ] satisfy 0 ⁇ A / B ⁇ 1 [cd ⁇ sr / W].
- visible light emission derived from the host material may be visually recognized.
- the light emission of the host material is light having a wavelength having low visibility.
- Examples of light having a wavelength having low luminosity factor include ultraviolet light to blue light and red light to near infrared light.
- the light emitting spectrum may further have a peak at 435 nm or less, or 565 nm or more and 900 nm or less.
- the wavelength of the peak is preferably 600 nm or more, and preferably 800 nm or less.
- the absorption band that is considered to contribute most to light emission is the absorption wavelength corresponding to the direct transition from the single-term ground state to the triple-term excited state. In the vicinity, it is the absorption band that appears on the longest wavelength side (low energy side). From this, it is preferable that the emission spectrum (fluorescence spectrum and phosphorescence spectrum) of the host material largely overlaps with the absorption band on the longest wavelength side (low energy side) of the absorption spectrum of the phosphorescence material. As a result, the excitation energy is smoothly transferred from the host material to the guest material. Then, the excitation energy of the host material is converted into the excitation energy of the guest material, so that the guest material emits light efficiently.
- the emission wavelength of the host material is a long wavelength.
- the light emitted from the host material is long-wavelength light, it is possible to realize a light emitting device that makes it difficult to visually recognize the emission of visible light (derived from the host material) and efficiently emits near-infrared light.
- the luminosity factor of the light emitted from the host material can be lowered, and the excitation energy is efficiently transferred from the host material to the guest material. Therefore, it is preferable.
- the HOMO level of the host material is preferably 0.4 eV or more higher than the HOMO level of the guest material. Since the HOMO level of the host material is sufficiently higher than the HOMO level of the guest material, the band gap of the host material can be reduced, so that the light emission can have a long wavelength. As a result, the luminosity factor of the light emission of the host material can be lowered. In addition, the transfer of excitation energy from the host material to the guest material occurs efficiently, and a light emitting device that efficiently emits near-infrared light can be realized.
- the LUMO level and HOMO level of the material can be derived from the electrochemical properties (reduction potential and oxidation potential) of the material measured by cyclic voltammetry (CV) measurement.
- the difference between the HOMO level and the LUMO level of the host material is preferably smaller than the difference between the HOMO level and the LUMO level of the guest material. Even if the difference between the HOMO level and the LUMO level of the host material is small, the emission of the host material can have a long wavelength.
- the difference between the HOMO level and the LUMO level in the host material is preferably 1.35 eV or more and 2.25 eV or less.
- the level difference is preferably 1.55 eV or more, and preferably 1.90 eV or less.
- the guest material using a phosphorescent material T 1 level position of the guest material than (the lowest energy level of a triplet excited state), the direction of T 1 level position of the host material is high, the light emitting device Luminous efficiency can be increased.
- the host material can convert the singlet excitation energy into light emission.
- S 1 level position of the host material (energy level of the lowest singlet excited state) is higher than each of T 1 level position of T 1 level position and the guest material of the host material. In order to make the emission of the host material from red light to near infrared light, it is preferable that the difference between the T 1 level of the guest material and the S 1 level of the host material is small.
- the difference between the S 1 level and T 1 level position of the host material is small.
- Thermally activated delayed fluorescence (Thermally Activated Delayed Fluorescence: TADF) material since the difference in S 1 level and T 1 level position is small, can be suitably used as the host material.
- a first organic compound and a second organic compound may be used as host materials in order to form an excited complex.
- the first organic compound and the second organic compound are combinations that form an excitation complex.
- the host material can also be said to be a mixed material of the first organic compound and the second organic compound.
- the light emitting device of one aspect of the present invention derives from an excitation complex formed by the first organic compound and the second organic compound. Light emission is confirmed. Therefore, in order to make the emission of the excitation complex less visible, it is preferable that the emission of the excitation complex is light having low luminosity factor.
- the height of the energy level is the HOMO level of the second organic compound ⁇ HOMO level of the first organic compound ⁇ LUMO level of the second organic compound ⁇ LUMO level of the first organic compound.
- the HOMO level of the first organic compound is preferably 0.4 eV or more higher than the HOMO level of the guest material.
- the emission of the excited complex can have a long wavelength.
- the luminosity factor of the excited complex can be lowered.
- the transfer of excitation energy from the excitation complex to the guest material occurs efficiently, and a light emitting device that efficiently emits near-infrared light can be realized.
- the difference between the HOMO level of the first organic compound and the LUMO level of the second organic compound is smaller than the difference between the HOMO level and the LUMO level of the guest material. Even if the difference between the HOMO level of the first organic compound and the LUMO level of the second organic compound is small, the emission of the excited complex can have a long wavelength.
- the difference between the HOMO level of the first organic compound and the LUMO level of the second organic compound is preferably 1.35 eV or more and 2.25 eV or less.
- the level difference is preferably 1.55 eV or more, and preferably 1.90 eV or less.
- the guest material preferably has a low emission intensity in the visible light region.
- the rising wavelength of the maximum peak on the short wavelength side in the light emitting spectrum is preferably 650 nm or more.
- tangent lines are drawn at each point on the curve from the point on the short wavelength side of the emission spectrum of the linear scale to the maximum point on the shortest wavelength side of the maximum points of the spectrum.
- the slope of this tangent increases as the curve rises (the value on the vertical axis increases).
- the wavelength at which the tangent line drawn at the point where this slope reaches the maximum value on the shortest wavelength side intersects the origin is defined as the rising wavelength.
- the maximum point where the value on the vertical axis is 10% or less of the maximum peak is excluded from the above-mentioned maximum point on the shortest wavelength side.
- the luminescent organic compound (guest material) preferably has a rising wavelength of 650 nm or more on the short wavelength side of the maximum peak of the photoluminescence (PL) spectrum in the solution.
- the external quantum efficiency of the light emitting device of one aspect of the present invention is preferably 1% or more.
- the light emitting intensity of the host material or the excitation complex is sufficiently low, so that the external quantum efficiency is the external quantum efficiency calculated from the light emitted from the guest material in the light emitting device, or It can be regarded as the external quantum efficiency calculated from the near-infrared emission in the light emitting device.
- the external quantum efficiency may be calculated using the data in a predetermined wavelength range. Specifically, the external quantum efficiency may be calculated from the data in the wavelength range of 600 nm or more and 1030 nm or less.
- the waveform separation of the emission spectrum may be performed to distinguish between the emission derived from the guest material and the emission derived from the host material or the excitation complex, and then the external quantum efficiency may be obtained.
- the external quantum efficiency calculated from the light emitted from the guest material is preferably 1% or more.
- the external quantum efficiency calculated from near-infrared emission in the light emitting device of one aspect of the present invention is preferably 1% or more.
- Luminous organic compounds are preferable because when they emit phosphorescence, the luminous efficiency in the light emitting device can be increased.
- the luminescent organic compound is preferably an organometallic complex having a metal-carbon bond.
- the luminescent organic compound is more preferably a cyclometal complex.
- the luminescent organic compound is preferably an orthometal complex. Since these organic compounds easily emit phosphorescence, the luminous efficiency in the light emitting device can be improved. Therefore, the light emitting device of one aspect of the present invention preferably emits phosphorescence.
- an organometallic complex having a metal-carbon bond is suitable as a luminescent organic compound because it has high luminescence efficiency and high chemical stability as compared with a porphyrin-based compound or the like.
- a large valley occurs in the absorption spectrum of the luminescent organic compound (a portion having low intensity occurs).
- the excitation energy is not smoothly transferred from the host material to the guest material, and the energy transfer efficiency is lowered.
- the absorption band derived from the triplet MLCT Metal to Ligand Charge Transfer
- the absorption band derived from the singlet MLCT transition and the triplet ⁇ - ⁇ * Since many absorption bands such as absorption bands derived from transitions overlap, large valleys are unlikely to occur in the absorption spectrum. Therefore, the range of excitation energy values of the material that can be used as the host material can be widened, and the range of selection of the host material can be widened.
- the luminescent organic compound is preferably an iridium complex.
- the luminescent organic compound is preferably a cyclometal complex using iridium as the central metal. Since the iridium complex has higher chemical stability than the platinum complex and the like, the reliability of the light emitting device can be improved by using the iridium complex as the luminescent organic compound. From the viewpoint of such stability, an iridium cyclometal complex is preferable, and an iridium orthometal complex is more preferable.
- the ligand in the organometallic complex preferably has a structure in which condensed heteroaromatic rings having 2 to 5 rings are coordinated to the metal.
- the condensed complex aromatic ring is preferably 3 or more rings.
- the condensed complex aromatic ring is preferably 4 rings or less. The more rings the fused complex aromatic ring has, the lower the LUMO level can be, and the longer the emission wavelength of the organometallic complex can be. Further, the smaller the number of fused complex aromatic rings, the higher the sublimation property.
- the LUMO level of the ligand is appropriately lowered, and while maintaining high sublimation property, the organic derived from the (triplet) MLCT transition.
- the emission wavelength of the metal complex can be extended to near infrared.
- the light emitting device of one aspect of the present invention can be formed in a film shape and can easily increase the area, it can be used as a surface light source that emits near infrared light.
- the light emitting device can hardly visually emit visible light and can efficiently emit near infrared light.
- a light emitting device By using such a light emitting device, it is possible to realize an electronic device that performs authentication, analysis, diagnosis, etc. using near infrared light.
- the electronic device In the electronic device, it is possible to suppress that the visible light emitted by the light emitting device becomes noise in authentication, analysis, diagnosis, etc. using near infrared light. As a result, the accuracy of authentication, analysis, diagnosis, etc. can be improved. Further, in electronic devices for security-related and military applications, imaging using near-infrared light can be performed without being noticed by people around.
- ⁇ Basic structure of light emitting device ⁇ 1A to 1C show an example of a light emitting device having an EL layer between a pair of electrodes.
- the light emitting device shown in FIG. 1A has a structure (single structure) in which the EL layer 103 is sandwiched between the first electrode 101 and the second electrode 102.
- the EL layer 103 has at least a light emitting layer.
- the light emitting device may have a plurality of EL layers between the pair of electrodes.
- FIG. 1B shows a light emitting device having a tandem structure having two EL layers (EL layer 103a and EL layer 103b) between a pair of electrodes and a charge generating layer 104 between the two EL layers.
- the light emitting device having a tandem structure can be driven at a low voltage and can reduce power consumption.
- the charge generation layer 104 injects electrons into one of the EL layer 103a and the EL layer 103b and creates holes in the other. Has the function of injecting. Therefore, in FIG. 1B, when a voltage is applied to the first electrode 101 so that the potential is higher than that of the second electrode 102, electrons are injected from the charge generation layer 104 into the EL layer 103a, and holes are injected into the EL layer 103b. Is injected.
- the charge generation layer 104 transmits near-infrared light from the viewpoint of light extraction efficiency (specifically, the transmittance of the charge generation layer 104 for near-infrared light is 40% or more). Is preferable. Further, the charge generation layer 104 functions even if the conductivity is lower than that of the first electrode 101 and the second electrode 102.
- FIG. 1C shows an example of the laminated structure of the EL layer 103.
- the EL layer 103 has a structure in which a hole injection layer 111, a hole transport layer 112, a light emitting layer 113, an electron transport layer 114, and an electron injection layer 115 are sequentially laminated on the first electrode 101.
- the hole injection layer 111, the hole transport layer 112, the light emitting layer 113, the electron transport layer 114, and the electron injection layer 115 may each have a single layer structure or a laminated structure. Even when a plurality of EL layers are provided as in the tandem structure shown in FIG. 1B, the same laminated structure as the EL layer 103 shown in FIG. 1C can be applied to each EL layer.
- the stacking order is reversed.
- the light emitting layer 113 has a light emitting substance or a plurality of substances in an appropriate combination, and can be configured to obtain fluorescent light emission or phosphorescent light emission having a desired wavelength.
- the EL layer 103a and the EL layer 103b shown in FIG. 1B may be configured to emit wavelengths different from each other.
- the light emitted from the EL layer may be resonated between the pair of electrodes to enhance the obtained light emission.
- the first electrode 101 is a reflecting electrode (an electrode having reflectivity to near-infrared light)
- the second electrode 102 is a semi-transmissive / semi-reflecting electrode (to near-infrared light).
- a micro-optical resonator (microcavity) structure can be formed, thereby enhancing the light emission obtained from the EL layer 103.
- the first electrode 101 of the light emitting device is a reflective electrode having a laminated structure of a conductive film having reflectivity for near-infrared light and a conductive film having translucency for near-infrared light.
- the optical adjustment can be performed by controlling the film thickness of the light-transmitting conductive film.
- the distance between the first electrode 101 and the second electrode 102 is close to m ⁇ / 2 (where m is a natural number) with respect to the wavelength ⁇ of the light obtained from the light emitting layer 113. It is preferable to adjust so as to.
- the optical distance from the first electrode 101 to the region (light emitting region) where the desired light of the light emitting layer 113 can be obtained, and the first. Adjust the optical distance from the electrode 102 of 2 to the region (light emitting region) where the desired light of the light emitting layer 113 is obtained so as to be close to (2 m'+ 1) ⁇ / 4 (however, m'is a natural number). It is preferable to do so.
- the light emitting region referred to here means a recombination region of holes and electrons in the light emitting layer 113.
- the spectrum of light obtained from the light emitting layer 113 can be narrowed, and light emission of a desired wavelength can be obtained.
- the optical distance between the first electrode 101 and the second electrode 102 is, strictly speaking, the total thickness from the reflection region of the first electrode 101 to the reflection region of the second electrode 102. it can.
- the optical distance between the first electrode 101 and the light emitting layer from which the desired light can be obtained is, strictly speaking, the optical distance between the reflection region at the first electrode 101 and the light emitting region at the light emitting layer where the desired light can be obtained. It can be said that it is a distance.
- an arbitrary position of the first electrode 101 can be set as the reflection region, which is desired. It is assumed that the above-mentioned effect can be sufficiently obtained by assuming that an arbitrary position of the light emitting layer from which light is obtained is a light emitting region.
- At least one of the first electrode 101 and the second electrode 102 is an electrode having translucency with respect to near-infrared light.
- the transmittance of the near-infrared light of the electrode having transparency to the near-infrared light is 40% or more.
- the electrode having translucency with respect to near-infrared light is the semi-transmissive / semi-reflecting electrode
- the reflectance of the near-infrared light of the electrode is 20% or more, preferably 40% or more. Further, it is less than 100%, preferably 95% or less, and may be 80% or less or 70% or less.
- the reflectance of near-infrared light of the electrode is 20% or more and 80% or less, preferably 40% or more and 70% or less.
- the resistivity of the electrode is preferably 1 ⁇ 10 -2 ⁇ cm or less.
- the reflectance of near-infrared light of the reflecting electrode is 40% or more and 100% or less, preferably 70% or more and 100% or less.
- the resistivity of this electrode is preferably 1 ⁇ 10 -2 ⁇ cm or less.
- the following materials can be appropriately combined and used as long as the functions of both electrodes described above can be satisfied.
- metals, alloys, electrically conductive compounds, and mixtures thereof can be appropriately used. Specific examples thereof include In—Sn oxide (also referred to as ITO), In—Si—Sn oxide (also referred to as ITSO), In—Zn oxide, and In—W—Zn oxide.
- Indium (In), Tin (Sn), Molybdenum (Mo), Tantal (Ta), Tungsten (W), Palladium (Pd), Gold (Au), Platinum (Pt), Silver (Ag), Yttrium (Y) ), Neodymium (Nd) and other metals, and alloys containing these in appropriate combinations can also be used.
- Other elements belonging to Group 1 or Group 2 of the Periodic Table of Elements not illustrated above eg, lithium (Li), cesium (Cs), calcium (Ca), strontium (Sr)), europium (Eu), ytterbium Rare earth metals such as (Yb) and alloys containing them in appropriate combinations, graphene and the like can be used.
- the first electrode 101 is formed as a reflective electrode
- the second electrode 102 is formed as a semitransmissive / semireflective electrode. Therefore, it can be formed in a single layer or laminated by using one or more desired conductive materials.
- the second electrode 102 is formed by selecting a material in the same manner as described above after forming the EL layer 103. Further, a sputtering method or a vacuum vapor deposition method can be used for producing these electrodes.
- the hole injection layer 111 and the hole transport layer 112 are sequentially laminated and formed on the first electrode 101 by a vacuum vapor deposition method.
- the hole injection layer 111 is a layer for injecting holes into the EL layer 103 from the first electrode 101, which is an anode, and is a layer containing a material having high hole injection properties.
- molybdenum oxide, vanadium oxide, ruthenium oxide, tungsten oxide, transition metal oxides such as manganese oxide, phthalocyanine (abbreviation: H 2 Pc) or copper phthalocyanine (abbreviation: A phthalocyanine-based compound such as CuPc) can be used.
- Materials with high hole injection properties include 4,4', 4'-tris (N, N-diphenylamino) triphenylamine (abbreviation: TDATA), 4,4', 4''-tris [N-]. (3-Methylphenyl) -N-phenylamino] triphenylamine (abbreviation: MTDATA), 4,4'-bis [N- (4-diphenylaminophenyl) -N-phenylamino] biphenyl (abbreviation: DPAB), 4,4'-Bis (N- ⁇ 4- [N'-(3-methylphenyl) -N'-phenylamino] phenyl ⁇ -N-phenylamino) Biphenyl (abbreviation: DNTPD), 1,3,5- Tris [N- (4-diphenylaminophenyl) -N-phenylamino] benzene (abbreviation: DPA3B), 3- [N- (9-pheny
- Materials with high hole injection properties include poly (N-vinylcarbazole) (abbreviation: PVK), poly (4-vinyltriphenylamine) (abbreviation: PVTPA), and poly [N- (4- ⁇ N'-[ 4- (4-Diphenylamino) phenyl] phenyl-N'-phenylamino ⁇ phenyl) methacrylamide] (abbreviation: PTPDMA), poly [N, N'-bis (4-butylphenyl) -N, N'-bis (Phenyl) benzidine] (abbreviation: Poly-TPD) and the like can be used.
- PVK poly (N-vinylcarbazole)
- PVTPA poly (4-vinyltriphenylamine)
- PTPDMA poly [N- (4- ⁇ N'-[ 4- (4-Diphenylamino) phenyl] phenyl-N'-phenylamino ⁇ phenyl) me
- a polymer compound to which an acid such as poly (3,4-ethylenedioxythiophene) / poly (styrene sulfonic acid) (abbreviation: PEDOT / PSS) or polyaniline / poly (styrene sulfonic acid) (Pani / PSS) is added. Etc. can also be used.
- a composite material containing a hole transporting material and an acceptor material can also be used.
- electrons are extracted from the hole transporting material by the acceptor material, holes are generated in the hole injection layer 111, and holes are injected into the light emitting layer 113 via the hole transport layer 112.
- the hole injection layer 111 may be formed of a single layer made of a composite material containing a hole transporting material and an acceptor material, and the hole transport material and the acceptor material may be formed of separate layers. It may be formed by laminating.
- the hole transport layer 112 is a layer that transports the holes injected from the first electrode 101 to the light emitting layer 113 by the hole injection layer 111.
- the hole transport layer 112 is a layer containing a hole transport material.
- oxides of metals belonging to Group 4 to Group 8 in the Periodic Table of the Elements can be used. Specific examples thereof include molybdenum oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, tungsten oxide, manganese oxide and rhenium oxide. Of these, molybdenum oxide is particularly preferable because it is stable in the atmosphere, has low hygroscopicity, and is easy to handle.
- organic acceptors such as quinodimethane derivatives, chloranil derivatives, and hexaazatriphenylene derivatives can be used.
- an electron-withdrawing group (a halogen group or a cyano group) is 7,7,8,8-(abbreviation: F 4 -TCNQ), chloranil, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (abbreviation: HAT-CN), 1,3,4,5,7,8-hexa Fluorotetracyano-naphthoquinodimethane (abbreviation: F6-TCNNQ) and the like can be mentioned.
- a compound such as HAT-CN in which an electron-withdrawing group is bonded to a condensed aromatic ring having a plurality of complex atoms is thermally stable and preferable.
- the [3] radialene derivative having an electron-withdrawing group is preferable because it has very high electron acceptability, and specifically, ⁇ , ⁇ ', ⁇ ''-.
- 1,2,3-Cyclopropanetriylidentris [4-cyano-2,3,5,6-tetrafluorobenzene acetonitrile], ⁇ , ⁇ ', ⁇ ''-1,2,3-cyclopropanetriiridentris [2,6-dichloro-3,5-difluoro-4- (trifluoromethyl) benzeneacetonitrile], ⁇ , ⁇ ', ⁇ ''-1,2,3-cyclopropanetriylidentris [2,3,4 , 5,6-Pentafluorobenzene acetonitrile] and the like.
- the hole transporting material used for the hole injection layer 111 and the hole transport layer 112 a substance having a hole mobility of 10-6 cm 2 / Vs or more is preferable.
- any substance other than these can be used as long as it is a substance having a higher hole transport property than electrons.
- the hole-transporting material examples include materials having high hole-transporting properties such as ⁇ -electron-rich heteroaromatic compounds (for example, carbazole derivatives, thiophene derivatives, furan derivatives, etc.) and aromatic amines (compounds having an aromatic amine skeleton). Is preferable.
- materials having high hole-transporting properties such as ⁇ -electron-rich heteroaromatic compounds (for example, carbazole derivatives, thiophene derivatives, furan derivatives, etc.) and aromatic amines (compounds having an aromatic amine skeleton). Is preferable.
- Examples of the carbazole derivative (compound having a carbazole skeleton) include a carbazole derivative (for example, a 3,3'-bicarbazole derivative), an aromatic amine having a carbazolyl group, and the like.
- bicarbazole derivative for example, 3,3'-bicarbazole derivative
- PCCP 3,3'-bis (9-phenyl-9H-carbazole)
- 9,9'-bis (1,1'-biphenyl-4-yl) -3,3'-bi-9H-carbazole
- 9,9'-bis (1,1'-biphenyl-3-yl) -3,3'-bi- 9H-carbazole
- 9- (2-naphthyl) -9'-phenyl-9H, 9'H-3,3'-bicarbazole abbreviation: ⁇ NCCP
- aromatic amine having a carbazolyl group examples include 4-phenyl-4'-(9-phenyl-9H-carbazole-3-yl) triphenylamine (abbreviation: PCBA1BP) and N- (4-biphenyl).
- PCBiF N- (1,1'-biphenyl-4-yl) ) -N- [4- (9-phenyl-9H-carbazole-3-yl) phenyl] -9,9-dimethyl-9H-fluoren-2-amine
- PCBBiF 4,4'-diphenyl-4 ''-(9-Phenyl-9H-carbazole-3-yl) triphenylamine
- PCBBi1BP 4- (1-naphthyl) -4'-(9-phenyl-9H-carbazole-3-yl) tri Phenylamine (abbreviation: PCBANB), 4,4'-di (1-naphthyl) -4''- (9-phenyl-9H-carbazole-3-yl) tri Phenylamine (abbreviation: PCBANB), 4,4'-di (1-naphthyl) -4''- (9-phenyl-9H-carbazol
- carbazole derivative examples include 3- [4- (9-phenanthryl) -phenyl] -9-phenyl-9H-carbazole (abbreviation: PCPPn) and 3- [4- (1-naphthyl) -phenyl] in addition to the above.
- PCPN 1,3-bis (N-carbazolyl) benzene
- mCP 1,3-bis (N-carbazolyl) benzene
- CBP 4,4'-di (N-carbazolyl) biphenyl
- CzTP 3,3,5-diphenylphenyl) -9-phenylcarbazole
- TCPB 1,3,5-tris [4- (N-carbazolyl) phenyl] benzene
- TCPB 1,3,5-tris [4- (N-carbazolyl) phenyl] benzene
- CzPA 9- [ 4- (10-phenyl-9-anthracenyl) phenyl] -9H-carbazole
- thiophene derivative compound having a thiophene skeleton
- furan derivative compound having a furan skeleton
- aromatic amine examples include 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (abbreviation: NPB or ⁇ -NPD) and N, N'-bis (3).
- polymer compounds such as PVK, PVTPA, PTPDMA, and Poly-TPD can also be used.
- the hole transporting material is not limited to the above, and various known materials can be used for the hole injection layer 111 and the hole transport layer 112 in combination of one or a plurality of known materials.
- the light emitting layer 113 is formed on the hole transport layer 112 by a vacuum vapor deposition method.
- the light emitting layer 113 is a layer containing a light emitting substance.
- the light emitting device of one aspect of the present invention has a luminescent organic compound as a light emitting substance.
- the luminescent organic compound emits near-infrared light.
- the maximum peak wavelength of light emitted by a luminescent organic compound is larger than 750 nm and 900 nm or less.
- a luminescent organic compound for example, bis ⁇ 4,6-dimethyl-2- [3- (3,5-dimethylphenyl)-, which is an organometallic complex shown as a guest material (phosphorescent material) in Examples described later.
- 2-Benzo [g] quinoxalinyl- ⁇ N] phenyl- ⁇ C ⁇ (2,2,6,6-tetramethyl-3,5-heptandionat- ⁇ 2 O, O') Iridium (III) (abbreviation: [Ir (dmdbpbq) ) 2 (dpm)]) can be used.
- luminescent organic compound for example, tetraphenyltetrabenzoporphyrin platinum (II) can be used.
- the light emitting layer 113 can have one or more kinds of light emitting substances.
- the light emitting layer 113 has one or more kinds of organic compounds (host material) in addition to the light emitting substance (guest material).
- the one or more kinds of organic compounds one or both of the hole transporting material and the electron transporting material described in this embodiment can be used. Further, a bipolar material may be used as one or more kinds of organic compounds.
- the luminescent material that can be used for the light emitting layer 113 is not particularly limited, and is a luminescent material that converts the singlet excitation energy into light emission in the near infrared light region, or a luminescent material that converts triplet excitation energy into light emission in the near infrared light region. Substances can be used.
- Examples of the luminescent substance that converts the single-term excitation energy into light emission include a substance that emits fluorescence (fluorescent material).
- examples thereof include quinoxalin derivatives, quinoxalin derivatives, pyridine derivatives, pyrimidine derivatives, phenanthrene derivatives and naphthalene derivatives.
- Examples of the luminescent substance that converts triplet excitation energy into light emission include a substance that emits phosphorescence (phosphorescent material) and a TADF material that exhibits thermal activated delayed fluorescence.
- an organic metal complex having a 4H-triazole skeleton, a 1H-triazole skeleton, an imidazole skeleton, a pyrimidine skeleton, a pyrazine skeleton, or a pyridine skeleton (particularly an iridium complex), or a phenylpyridine derivative having an electron-withdrawing group is arranged.
- examples thereof include an organic metal complex (particularly an iridium complex), a platinum complex, and a rare earth metal complex as a ligand.
- one or a plurality of substances having an energy gap larger than the energy gap of the light emitting substance can be selected and used.
- the organic compound used in combination with the luminescent material has a large energy level in the singlet excited state and a small energy level in the triplet excited state. Is preferable.
- the organic compounds that can be used in combination with the luminescent material include anthracene derivatives, tetracene derivatives, phenanthrene derivatives, pyrene derivatives, chrysene derivatives, and dibenzo [g, p] chrysene derivatives. Examples include ring aromatic compounds.
- organic compound (host material) used in combination with the fluorescent material examples include 9-phenyl-3- [4- (10-phenyl-9-anthryl) phenyl] -9H-carbazole (abbreviation: PCzPA), 3, 6-Diphenyl-9- [4- (10-phenyl-9-anthryl) phenyl] -9H-carbazole (abbreviation: DPCzPA), PCPN, 9,10-diphenylanthracene (abbreviation: DPAnth), N, N-diphenyl- 9- [4- (10-phenyl-9-anthryl) phenyl] -9H-carbazole-3-amine (abbreviation: CzA1PA), 4- (10-phenyl-9-anthryl) triphenylamine (abbreviation: DPhPA), 4- (9H-carbazole-9-yl) -4'-(10-phenyl-9-anthril) triphenylamine (abbreviation: PC
- the organic compound used in combination with the luminescent material is an organic compound having a triplet excitation energy larger than the triplet excitation energy (energy difference between the base state and the triplet excited state) of the luminescent material. You just have to select.
- a plurality of organic compounds for example, a first host material and a second host material
- a luminescent material for example, a phosphorescent material
- these multiple organic compounds are used as a phosphorescent material (particularly an organometallic complex). ) And it is preferable to use it.
- ExTET Extra-Triplet Energy Transfer
- the combination of a plurality of organic compounds is preferably one in which an excitation complex is easily formed, and a compound that easily receives holes (hole transporting material) and a compound that easily receives electrons (electron transporting material) are combined. Is particularly preferred.
- the hole transporting material and the electron transporting material the materials shown in the present embodiment can be used. With this configuration, high efficiency, low voltage, and long life of the light emitting device can be realized at the same time.
- Examples of the organic compound that can be used in combination with the luminescent substance when the luminescent substance is a phosphorescent material include aromatic amines, carbazole derivatives, dibenzothiophene derivatives, dibenzofuran derivatives, zinc and aluminum-based metal complexes, and oxadiazole derivatives.
- Examples thereof include triazole derivatives, benzoimidazole derivatives, quinoxalin derivatives, dibenzoquinoxalin derivatives, pyrimidine derivatives, triazine derivatives, pyridine derivatives, bipyridine derivatives, phenanthroline derivatives and the like.
- aromatic amines compounds having an aromatic amine skeleton
- carbazole derivatives dibenzothiophene derivatives (thiophene derivatives)
- dibenzofuran derivatives dibenzofuran derivatives (furan derivatives)
- hole transporting material shown above.
- zinc and aluminum-based metal complexes that are organic compounds with high electron transport properties include tris (8-quinolinolato) aluminum (III) (abbreviation: Alq) and tris (4-methyl-8-quinolinolato) aluminum.
- III) abbreviation: Almq 3
- bis (10-hydroxybenzo [h] quinolinato) berylium (II) abbreviation: BeBq 2
- metal complexes having a quinoline skeleton or a benzoquinolin skeleton such as (III) (abbreviation: BAlq) and bis (8-quinolinolato) zinc (II) (abbreviation: Znq).
- oxazoles such as bis [2- (2-benzothazolyl) phenolato] zinc (II) (abbreviation: ZnPBO) and bis [2- (2-benzothiazolyl) phenolato] zinc (II) (abbreviation: ZnBTZ)
- ZnPBO bis [2- (2-benzothazolyl) phenolato] zinc
- ZnBTZ bis [2- (2-benzothiazolyl) phenolato] zinc
- oxadiazole derivative triazole derivative
- benzoimidazole derivative benzoimidazole derivative
- quinoxalin derivative dibenzoquinoxalin derivative
- phenylanthrolin derivative which are organic compounds having high electron transport properties
- heterocyclic compound having a diazine skeleton the heterocyclic compound having a triazine skeleton, and the heterocyclic compound having a pyridine skeleton, which are organic compounds having high electron transport properties, are 4,6-bis [3- (phenanthrene-).
- organic compounds having high electron transport properties examples include poly (2,5-pyridinediyl) (abbreviation: PPy) and poly [(9,9-dihexylfluorene-2,7-diyl) -co- (pyridine-3,5). -Diyl)] (abbreviation: PF-Py), poly [(9,9-dioctylfluorene-2,7-diyl) -co- (2,2'-bipyridine-6,6'-diyl)] (abbreviation: A high molecular compound such as PF-BPy) can also be used.
- the TADF material is a material that has a small difference between the S 1 level and the T 1 level and has a function of converting energy from triplet excitation energy to singlet excitation energy by intersystem crossing. Therefore, the triplet excited energy can be up-converted to the singlet excited energy by a small amount of heat energy (intersystem crossing), and the singlet excited state can be efficiently generated. In addition, triplet excitation energy can be converted into light emission.
- the conditions for thermally activated delayed fluorescence is efficiently obtained, the energy difference between the S 1 level and T 1 level position is 0eV than 0.2eV or less, preferably not more than 0.1eV than 0eV.
- delayed fluorescence in TADF materials refers to emission that has a spectrum similar to that of normal fluorescence but has a significantly long lifetime. Its life is 10-6 seconds or longer, preferably 10-3 seconds or longer.
- a phosphorescence spectrum observed at a low temperature may be used as an index of the T 1 level.
- the TADF material drawing a tangential line at the short wavelength side of the hem of the fluorescence spectrum, the energy of the wavelength of the extrapolation and S 1 levels, drawing a tangential line at the short wavelength side of the hem of the phosphorescence spectrum, its extrapolation the energy of the wavelength of the line upon the T 1 level position, it is preferable that difference between the S 1 level and T 1 level position is below 0.3 eV, and more preferably less 0.2 eV.
- the TADF material may be used as a guest material or as a host material.
- Examples of the TADF material include fullerenes and derivatives thereof, acridine derivatives such as proflavin, and eosin.
- Examples thereof include metal-containing porphyrins containing magnesium (Mg), zinc (Zn), cadmium (Cd), tin (Sn), platinum (Pt), indium (In), palladium (Pd) and the like.
- Examples of the metal-containing porphyrin include protoporphyrin-tin fluoride complex (abbreviation: SnF 2 (Proto IX)), mesoporphyrin-tin fluoride complex (abbreviation: SnF 2 (Meso IX)), and hematoporphyrin-tin fluoride.
- a heterocyclic compound having can be used.
- a substance in which a ⁇ -electron-rich heteroaromatic ring and a ⁇ -electron-deficient heteroaromatic ring are directly bonded has a stronger donor property of the ⁇ -electron-rich heteroaromatic ring and a stronger acceptability of the ⁇ -electron-deficient heteroaromatic ring. , It is particularly preferable because the energy difference between the single-term excited state and the triple-term excited state becomes small.
- TADF material When a TADF material is used, it can also be used in combination with other organic compounds. In particular, it can be combined with the host material, hole transport material, and electron transport material described above.
- the above material can be used for forming the light emitting layer 113 by combining with a low molecular weight material or a high molecular weight material. Further, a known method (evaporation method, coating method, printing method, etc.) can be appropriately used for film formation.
- the electron transport layer 114 is formed on the light emitting layer 113.
- the electron transport layer 114 is a layer that transports the electrons injected from the second electrode 102 to the light emitting layer 113 by the electron injection layer 115.
- the electron transport layer 114 is a layer containing an electron transport material.
- the electron-transporting material used for the electron-transporting layer 114 is preferably a substance having an electron mobility of 1 ⁇ 10-6 cm 2 / Vs or more. In addition, any substance other than these can be used as long as it is a substance having a higher electron transport property than holes.
- Examples of the electron-transporting material include a metal complex having a quinoline skeleton, a metal complex having a benzoquinoline skeleton, a metal complex having an oxazole skeleton, a metal complex having a thiazole skeleton, and the like, as well as an oxazole derivative, a triazole derivative, and an imidazole derivative.
- ⁇ electron deficiency including oxazole derivative, thiazole derivative, phenanthroline derivative, quinoline derivative having quinoline ligand, benzoquinoline derivative, quinoxalin derivative, dibenzoquinoxaline derivative, pyridine derivative, bipyridine derivative, pyrimidine derivative, and other nitrogen-containing heteroaromatic compounds
- a material having high electron transport property such as a type heteroaromatic compound can be used.
- the material shown above can be used.
- an electron injection layer 115 is formed on the electron transport layer 114 by a vacuum vapor deposition method.
- the electron injection layer 115 is a layer containing a substance having a high electron injection property.
- the electron injection layer 115 contains an alkali metal such as lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF 2 ), lithium oxide (LiO x ), or an alkaline earth metal, or the like. Compounds can be used. In addition, rare earth metal compounds such as erbium fluoride (ErF 3 ) can be used. Further, an electlide may be used for the electron injection layer 115. Examples of the electride include a substance in which a high concentration of electrons is added to a mixed oxide of calcium and aluminum. The substance constituting the electron transport layer 114 described above can also be used.
- a composite material containing an electron transporting material and a donor material may be used for the electron injection layer 115.
- a composite material is excellent in electron injection property and electron transport property because electrons are generated in the organic compound by the electron donor.
- the organic compound is preferably a material excellent in transporting generated electrons, and specifically, for example, an electron transporting material (metal complex, heteroaromatic compound, etc.) used for the above-mentioned electron transport layer 114. ) Can be used.
- the electron donor may be any substance that exhibits electron donating property to the organic compound.
- alkali metals, alkaline earth metals and rare earth metals are preferable, and lithium, cesium, magnesium, calcium, erbium, ytterbium and the like can be mentioned.
- alkali metal oxides and alkaline earth metal oxides are preferable, and lithium oxides, calcium oxides, barium oxides and the like can be mentioned.
- a Lewis base such as magnesium oxide can also be used.
- an organic compound such as tetrathiafulvalene (abbreviation: TTF) can also be used.
- the charge generation layer 104 injects electrons into the EL layer 103a when a voltage is applied between the first electrode 101 (anode) and the second electrode 102 (cathode). , Has a function of injecting holes into the EL layer 103b.
- the charge generation layer 104 may have a structure including a hole transporting material and an acceptor material (electron acceptor material), or may have a structure including an electron transporting material and a donor material. By forming the charge generation layer 104 having such a configuration, it is possible to suppress an increase in the drive voltage when the EL layers are laminated.
- the hole transporting material As the hole transporting material, the accepting material, the electron transporting material, and the donor material, the above-mentioned materials can be used.
- a vacuum process such as a vapor deposition method or a solution process such as a spin coating method or an inkjet method can be used to fabricate the light emitting device shown in the present embodiment.
- a physical vapor deposition method PVD method
- a sputtering method such as a sputtering method, an ion plating method, an ion beam vapor deposition method, a molecular beam deposition method, or a vacuum vapor deposition method, or a chemical vapor deposition method (CVD method) is used.
- PVD method physical vapor deposition method
- CVD method chemical vapor deposition method
- a vapor deposition method vacuum vapor deposition method, etc.
- a coating method dip
- Coating method die coating method, bar coating method, spin coating method, spray coating method, etc.
- printing method inkprint method, screen (hole plate printing) method, offset (flat plate printing) method, flexo (letter plate printing) method, gravure method, It can be formed by a method such as microcontact method).
- the materials of the functional layer and the charge generation layer constituting the EL layer 103 are not limited to the above-mentioned materials, respectively.
- a high molecular compound oligoform, dendrimer, polymer, etc.
- a medium molecular compound compound in the intermediate region between low molecular weight and high molecular weight: molecular weight 400 to 4000
- an inorganic compound quantum dot material, etc.
- a colloidal quantum dot material an alloy type quantum dot material, a core / shell type quantum dot material, a core type quantum dot material, or the like can be used.
- the light emitting device of one aspect of the present invention it is difficult to visually recognize the light emission of the host material or the excitation complex formed by the host material. Therefore, it is possible to realize a light emitting device that makes it difficult to visually recognize the light emission of visible light and efficiently emits near infrared light.
- the brightness A [cd / m 2 ] and the radiance B [W / sr / m 2 ] are 0 ⁇ A / B ⁇ 1 [cd ⁇ sr / W] (or 0 ⁇ A / B ⁇ 1 [cd ⁇ sr / W]) is satisfied. Therefore, it is possible to realize a light emitting device that makes it difficult to visually recognize the light emission of visible light and efficiently emits near infrared light.
- the light emitting device of the present embodiment has the light emitting device shown in the first embodiment. Therefore, it is possible to realize a light emitting device that emits near-infrared light and makes it difficult to visually recognize the light emission of visible light.
- FIGS. 2A and 2C show a cross-sectional view between the alternate long and short dash lines X1-Y1 and X2-Y2 of FIG. 2A.
- the light emitting device shown in FIGS. 2A to 2C can be used, for example, in a lighting device.
- the light emitting device may be any of bottom emission, top emission, and dual emission.
- the light emitting device shown in FIG. 2B includes a substrate 490a, a substrate 490b, a conductive layer 406, a conductive layer 416, an insulating layer 405, an organic EL device 450 (first electrode 401, EL layer 402, and second electrode 403), and It has an adhesive layer 407.
- the organic EL device 450 the light emitting device shown in the first embodiment can be used.
- the organic EL device 450 has a first electrode 401 on the substrate 490a, an EL layer 402 on the first electrode 401, and a second electrode 403 on the EL layer 402.
- the organic EL device 450 is sealed by the substrate 490a, the adhesive layer 407, and the substrate 490b.
- the ends of the first electrode 401, the conductive layer 406, and the conductive layer 416 are covered with the insulating layer 405.
- the conductive layer 406 is electrically connected to the first electrode 401, and the conductive layer 416 is electrically connected to the second electrode 403.
- the conductive layer 406 covered with the insulating layer 405 via the first electrode 401 functions as an auxiliary wiring and is electrically connected to the first electrode 401. It is preferable to have an auxiliary wiring electrically connected to the electrode of the organic EL device 450 because the voltage drop due to the resistance of the electrode can be suppressed.
- the conductive layer 406 may be provided on the first electrode 401. Further, an auxiliary wiring for electrically connecting to the second electrode 403 may be provided on the insulating layer 405 or the like.
- Glass, quartz, ceramic, sapphire, organic resin and the like can be used for the substrate 490a and the substrate 490b, respectively.
- the flexibility of the light emitting device can be increased.
- a light extraction structure for improving the light extraction efficiency, an antistatic film for suppressing the adhesion of dust, a water-repellent film for preventing the adhesion of dirt, and a hardware for suppressing the occurrence of scratches due to use.
- a coat film, a shock absorbing layer, or the like may be arranged.
- Examples of the insulating material that can be used for the insulating layer 405 include resins such as acrylic resin and epoxy resin, and inorganic insulating materials such as silicon oxide, silicon oxide, silicon nitride, silicon nitride, and aluminum oxide.
- various curable adhesives such as a photocurable adhesive such as an ultraviolet curable type, a reaction curable type adhesive, a thermosetting type adhesive, and an anaerobic type adhesive can be used.
- these adhesives include epoxy resin, acrylic resin, silicone resin, phenol resin, polyimide resin, imide resin, PVC (polyvinyl chloride) resin, PVB (polyvinyl butyral) resin, EVA (ethylene vinyl acetate) resin and the like.
- a material having low moisture permeability such as an epoxy resin is preferable.
- a two-component mixed type resin may be used.
- the light emitting device shown in FIG. 2C has a barrier layer 490c, a conductive layer 406, a conductive layer 416, an insulating layer 405, an organic EL device 450, an adhesive layer 407, a barrier layer 423, and a substrate 490b.
- the barrier layer 490c shown in FIG. 2C has a substrate 420, an adhesive layer 422, and an insulating layer 424 having a high barrier property.
- the organic EL device 450 is arranged between the insulating layer 424 having a high barrier property and the barrier layer 423. Therefore, even if a resin film or the like having a relatively low waterproof property is used for the substrate 420 and the substrate 490b, it is possible to prevent impurities such as water from entering the organic EL device and shortening the life.
- the substrate 420 and the substrate 490b are provided with polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyacrylonitrile resin, acrylic resin, polyimide resin, polymethylmethacrylate resin, and polycarbonate (PC) resin, respectively.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PC polycarbonate
- Polyether sulfone (PES) resin polyamide resin (nylon, aramid, etc.), polysiloxane resin, cycloolefin resin, polystyrene resin, polyamideimide resin, polyurethane resin, polyvinyl chloride resin, polyvinylidene chloride resin, polypropylene resin, polytetra Fluoroethylene (PTFE) resin, ABS resin, cellulose nanofibers and the like can be used.
- glass having a thickness sufficient to have flexibility may be used.
- the insulating layer 424 having a high barrier property it is preferable to use an inorganic insulating film.
- an inorganic insulating film for example, a silicon nitride film, a silicon nitride film, a silicon oxide film, a silicon nitride film, an aluminum oxide film, an aluminum nitride film, or the like can be used. Further, a hafnium oxide film, an yttrium oxide film, a zirconium oxide film, a gallium oxide film, a tantalum oxide film, a magnesium oxide film, a lanthanum oxide film, a cerium oxide film, a neodymium oxide film and the like may be used. Further, two or more of the above-mentioned insulating films may be laminated and used.
- the barrier layer 423 preferably has at least one inorganic film.
- a single-layer structure of an inorganic film or a laminated structure of an inorganic film and an organic film can be applied to the barrier layer 423.
- the inorganic film the above-mentioned inorganic insulating film is suitable.
- the laminated structure include a structure in which a silicon oxide film, a silicon oxide film, an organic film, a silicon oxide film, and a silicon nitride film are formed in this order.
- the highly barrier insulating layer 424 and the organic EL device 450 can be formed directly on the flexible substrate 420. In this case, the adhesive layer 422 is unnecessary. Further, the insulating layer 424 and the organic EL device 450 can be transferred to the substrate 420 after being formed on the hard substrate via the release layer. For example, the insulating layer 424 and the organic EL device 450 are peeled from the hard substrate by applying heat, force, laser light, or the like to the peeling layer, and then the substrate 420 is bonded to the peeling layer using the adhesive layer 422. It may be transposed to.
- the release layer for example, a laminated structure of an inorganic film containing a tungsten film and a silicon oxide film, an organic resin film such as polyimide, or the like can be used.
- the insulating layer 424 can be formed by applying a high temperature as compared with a resin substrate or the like, so that the insulating layer 424 can be a dense and extremely barrier insulating film.
- the light emitting device of one aspect of the present invention can be a passive matrix type or an active matrix type.
- the active matrix type light emitting device will be described with reference to FIG.
- FIG. 3A shows a top view of the light emitting device.
- FIG. 3B is a cross-sectional view between the alternate long and short dash lines AA'shown in FIG. 3A.
- the active matrix type light emitting device shown in FIGS. 3A and 3B includes a pixel unit 302, a circuit unit 303, a circuit unit 304a, and a circuit unit 304b.
- the circuit unit 303, the circuit unit 304a, and the circuit unit 304b can each function as a scanning line drive circuit (gate driver) or a signal line drive circuit (source driver).
- the circuit may be a circuit that electrically connects the external gate driver or source driver and the pixel unit 302.
- a routing wiring 307 is provided on the first substrate 301.
- the routing wiring 307 is electrically connected to the FPC 308 which is an external input terminal.
- the FPC 308 transmits an external signal (for example, a video signal, a clock signal, a start signal, a reset signal, etc.) or an electric potential to the circuit unit 303, the circuit unit 304a, and the circuit unit 304b.
- a printed wiring board may be attached to the FPC 308.
- the configuration shown in FIGS. 3A and 3B can also be said to be a light emitting module having a light emitting device (or light emitting device) and an FPC.
- the pixel unit 302 has a plurality of pixels having an organic EL device 317, a transistor 311 and a transistor 312.
- the organic EL device 317 the light emitting device shown in the first embodiment can be used.
- the transistor 312 is electrically connected to the first electrode 313 of the organic EL device 317.
- the transistor 311 functions as a switching transistor.
- the transistor 312 functions as a current control transistor.
- the number of transistors included in each pixel is not particularly limited, and can be appropriately provided as needed.
- the circuit unit 303 has a plurality of transistors including a transistor 309, a transistor 310, and the like.
- the circuit unit 303 may be formed of a circuit including a unipolar (only one of N-type or P-type) transistors, or may be formed of a CMOS circuit including an N-type transistor and a P-type transistor. Good. Further, the configuration may have a drive circuit externally.
- the structure of the transistor included in the light emitting device of the present embodiment is not particularly limited.
- a planar type transistor, a stagger type transistor, an inverted stagger type transistor and the like can be used.
- either a top gate type or a bottom gate type transistor structure may be used.
- gates may be provided above and below the semiconductor layer on which the channel is formed.
- the crystallinity of the semiconductor material used for the transistor is also not particularly limited, and either an amorphous semiconductor or a semiconductor having crystallinity (microcrystalline semiconductor, polycrystalline semiconductor, single crystal semiconductor, or semiconductor having a partially crystalline region). May be used. It is preferable to use a semiconductor having crystallinity because deterioration of transistor characteristics can be suppressed.
- the semiconductor layer of the transistor preferably has a metal oxide (also referred to as an oxide semiconductor).
- the semiconductor layer of the transistor may have silicon. Examples of silicon include amorphous silicon and crystalline silicon (low temperature polysilicon, single crystal silicon, etc.).
- the semiconductor layers include, for example, indium and M (M is gallium, aluminum, silicon, boron, ittrium, tin, copper, vanadium, beryllium, titanium, iron, nickel, germanium, zirconium, molybdenum, lantern, cerium, neodymium, etc. It is preferable to have one or more selected from hafnium, tantalum, tungsten, and gallium) and zinc.
- M is preferably one or more selected from aluminum, gallium, yttrium, and tin.
- an oxide containing indium (In), gallium (Ga), and zinc (Zn) also referred to as IGZO
- IGZO oxide containing indium (In), gallium (Ga), and zinc (Zn)
- the sputtering target used for forming the In-M-Zn oxide preferably has an In atom ratio of M or more.
- the transistor included in the circuit unit 303, the circuit unit 304a, and the circuit unit 304b and the transistor included in the pixel unit 302 may have the same structure or different structures.
- the structures of the plurality of transistors included in the circuit unit 303, the circuit unit 304a, and the circuit unit 304b may all be the same, or may be two or more types.
- the structures of the plurality of transistors included in the pixel unit 302 may all be the same, or there may be two or more types.
- the end of the first electrode 313 is covered with an insulating layer 314.
- an organic compound such as a negative type photosensitive resin or a positive type photosensitive resin (acrylic resin), or an inorganic compound such as silicon oxide, silicon oxide nitride, or silicon nitride can be used.
- the upper end portion or the lower end portion of the insulating layer 314 has a curved surface having a curvature. Thereby, the covering property of the film formed on the upper layer of the insulating layer 314 can be improved.
- An EL layer 315 is provided on the first electrode 313, and a second electrode 316 is provided on the EL layer 315.
- the EL layer 315 has a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a charge generation layer, and the like.
- the plurality of transistors and the plurality of organic EL devices 317 are sealed by the first substrate 301, the second substrate 306, and the sealing material 305.
- the space 318 surrounded by the first substrate 301, the second substrate 306, and the sealing material 305 may be filled with an inert gas (nitrogen, argon, etc.) or an organic substance (including the sealing material 305).
- Epoxy resin or glass frit can be used for the sealing material 305.
- the sealing material 305 is preferably made of a material that does not allow moisture or oxygen to permeate as much as possible.
- a glass frit is used as the sealing material, it is preferable that the first substrate 301 and the second substrate 306 are glass substrates from the viewpoint of adhesiveness.
- the light emitting device of one aspect of the present invention emits near-infrared light, and the light emission of visible light is difficult to visually recognize.
- a light emitting device it is possible to realize an electronic device that performs authentication, analysis, diagnosis, etc. using near infrared light.
- the electronic device it is possible to suppress that the visible light emitted by the light emitting device becomes noise in authentication, analysis, diagnosis, etc. using near infrared light.
- the accuracy of authentication, analysis, diagnosis, etc. can be improved.
- imaging using near-infrared light can be performed without being noticed by people around.
- FIG. 4A is a biometric authentication device for a finger vein, which has a housing 911, a light source 912, a detection stage 913, and the like. By placing a finger on the detection stage 913, the shape of the vein can be imaged.
- a light source 912 that emits near-infrared light is installed in the upper part of the detection stage 913, and an image pickup device 914 is installed in the lower part.
- the detection stage 913 is made of a material that transmits near-infrared light, and the near-infrared light that is emitted from the light source 912 and transmitted through the finger can be imaged by the image pickup apparatus 914.
- An optical system may be provided between the detection stage 913 and the image pickup apparatus 914.
- the configuration of the above device can also be used for a biometric authentication device for a vein in the palm.
- the light emitting device of one aspect of the present invention can be used for the light source 912.
- the light emitting device according to one aspect of the present invention can be installed in a curved shape, and can uniformly irradiate an object with light.
- a light emitting device that emits near-infrared light having the strongest peak intensity at a wavelength of 760 nm or more and 900 nm or less is preferable.
- the position of a vein can be detected by receiving light transmitted through a finger or palm and imaging it. The action can be used as biometric authentication. Further, by combining with the global shutter method, highly accurate sensing becomes possible even if the subject moves.
- the light source 912 can have a plurality of light emitting units as shown in the light emitting units 915, 916, and 917 shown in FIG. 4B.
- Each of the light emitting units 915, 916, and 917 may emit light at a different wavelength, and each may irradiate light at different timings. Therefore, since different images can be continuously captured by changing the wavelength and angle of the emitted light, a plurality of images can be used for authentication and high security can be realized.
- FIG. 4C is a biometric authentication device for a vein in the palm, which includes a housing 921, an operation button 922, a detection unit 923, a light source 924 that emits near-infrared light, and the like.
- the shape of the vein in the palm can be recognized by holding a hand over the detection unit 923. You can also enter a password or the like using the operation buttons.
- a light source 924 is arranged around the detection unit 923 to irradiate an object (hand). Then, the reflected light from the object is incident on the detection unit 923.
- the light emitting device of one aspect of the present invention can be used for the light source 924.
- An imaging device 925 is arranged directly below the detection unit 923, and an image of an object (overall image of the hand) can be captured.
- An optical system may be provided between the detection unit 923 and the image pickup device 925.
- the configuration of the above device can also be used for a biometric authentication device for a finger vein.
- FIG. 4D is a non-destructive inspection device, which includes a housing 931, an operation panel 932, a transport mechanism 933, a monitor 934, a detection unit 935, a light source 938 that emits near infrared light, and the like.
- the light emitting device of one aspect of the present invention can be used for the light source 938.
- the member to be inspected 936 is transported directly under the detection unit 935 by the transport mechanism 933.
- the member to be inspected 936 is irradiated with near-infrared light from the light source 938, and the transmitted light is imaged by an image pickup device 937 provided in the detection unit 935.
- the captured image is displayed on the monitor 934.
- FIG. 4E is a mobile phone, which includes a housing 981, a display unit 982, an operation button 983, an external connection port 984, a speaker 985, a microphone 986, a first camera 987, a second camera 988, and the like.
- the mobile phone includes a touch sensor on the display unit 982.
- the housing 981 and the display unit 982 are flexible. All operations such as making a phone call or inputting characters can be performed by touching the display unit 982 with a finger or a stylus.
- the first camera 987 can acquire a visible light image
- the second camera 988 can acquire an infrared light image (near infrared light image).
- the mobile phone or display 982 shown in FIG. 4E may have a light emitting device according to an aspect of the present invention.
- results of producing and evaluating a device 1 to which one aspect of the present invention is applied and a comparison device 2 for comparison will be described as light emitting devices.
- the structures of the device 1 and the comparison device 2 used in this embodiment are shown in FIG. 5, and the specific configuration is shown in Table 1.
- the chemical formulas of the materials used in this example are shown below.
- a first electrode 801 is formed on the substrate 800, and a hole injection layer is formed on the first electrode 801 as an EL layer 802. It has a structure in which 811, a hole transport layer 812, a light emitting layer 813, an electron transport layer 814, and an electron injection layer 815 are sequentially laminated, and a second electrode 803 is laminated on the electron injection layer 815.
- the first electrode 801 was formed on the substrate 800.
- the electrode area was 4 mm 2 (2 mm ⁇ 2 mm).
- a glass substrate was used as the substrate 800.
- the first electrode 801 was formed by forming a film of indium tin oxide (ITSO) containing silicon oxide by a sputtering method.
- the film thickness of the first electrode 801 was 70 nm for the device 1 and 110 nm for the comparative device 2.
- the first electrode 801 functions as an anode.
- the surface of the substrate was washed with water, fired at 200 ° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.
- the substrate was introduced into a vacuum vapor deposition apparatus whose internal pressure was reduced to about 1 ⁇ 10 -4 Pa, and the substrate was vacuum-fired at 170 ° C. for 30 minutes in a heating chamber inside the vacuum vapor deposition apparatus for 30 minutes. Allowed to cool.
- the hole injection layer 811 was formed on the first electrode 801.
- the hole injection layer 811 is formed by reducing the pressure in the vacuum vapor deposition apparatus to about 1 ⁇ 10 -4 Pa, and then using 1,3,5-tri (dibenzothiophen-4-yl) benzene (abbreviation: DBT3P-II) and molybdenum oxide.
- the film thickness of the hole injection layer 811 was 120 nm for device 1 and 60 nm for comparative device 2.
- the hole transport layer 812 was formed on the hole injection layer 811.
- the hole transport layer 812 is composed of N- (1,1'-biphenyl-4-yl) -N- [4- (9-phenyl-9H-carbazole-3-yl) phenyl] -9,9-dimethyl-9H. It was formed by vapor deposition using ⁇ fluorene-2-amine (abbreviation: PCBBiF) so as to have a film thickness of 20 nm.
- PCBBiF ⁇ fluorene-2-amine
- a light emitting layer 813 was formed on the hole transport layer 812.
- an electron transport layer 814 was formed on the light emitting layer 813.
- the electron transport layer 814 of the device 1 has a film thickness of 2.8 mDBtP2Bfqn of 20 nm and a film thickness of 2,9-bis (naphthalene-2-yl) -4,7-diphenyl-1,10-phenanthroline (abbreviation: NBphenyl). It was formed by successive vapor deposition so that the thickness was 70 nm.
- the electron transport layer 814 of the comparative device 2 was formed by thin-film deposition so that the film thickness of 2mDBTBPDBq-II was 20 nm and the film thickness of NBphen was 70 nm.
- an electron injection layer 815 was formed on the electron transport layer 814.
- the electron injection layer 815 was formed by vapor deposition using lithium fluoride (LiF) so as to have a film thickness of 1 nm.
- a second electrode 803 was formed on the electron injection layer 815.
- the second electrode 803 was formed by a vapor deposition method of aluminum so as to have a film thickness of 200 nm.
- the second electrode 803 functions as a cathode.
- a light emitting device formed by sandwiching the EL layer 802 between a pair of electrodes is formed on the substrate 800.
- the hole injection layer 811, the hole transport layer 812, the light emitting layer 813, the electron transport layer 814, and the electron injection layer 815 described in the above steps are functional layers constituting the EL layer in one aspect of the present invention. Further, in all the vapor deposition steps in the above-mentioned production method, the vapor deposition method by the resistance heating method was used.
- the light emitting device manufactured as shown above is sealed by another substrate (not shown).
- another substrate (not shown) coated with an adhesive that is solidified by ultraviolet light is placed on the substrate 800 in a glove box having a nitrogen atmosphere.
- the substrates were fixed and the substrates were adhered to each other so that the adhesive adhered around the light emitting device formed on the substrate 800.
- the adhesive was stabilized by irradiating it with ultraviolet light of 365 nm 2 at 6 J / cm 2 to solidify the adhesive and heat-treating it at 80 ° C. for 1 hour.
- ⁇ Operating characteristics of light emitting device ⁇ The operating characteristics of device 1 and comparison device 2 were measured. The measurement was performed at room temperature (atmosphere maintained at 25 ° C.).
- FIG. 6 and 7 show the emission spectra when a current is passed through the device 1 and the comparison device 2 at a current density of 50 mA / cm 2 .
- the range of wavelength 380 nm or more and 749 nm or less is the measurement result using a spectroradiance meter (SR-UL1R, manufactured by Topcon)
- the range of wavelength 750 nm or more and 1030 nm or less is a near infrared spectroradiometer (SR-UL1R, manufactured by Topcon). It is a measurement result using SR-NIR (manufactured by Topcon).
- FIG. 7 is different from FIG. 6 in that the vertical axis is a logarithmic display. Further, FIG. 7 also shows a scotopic vision curve based on scotopic luminosity (CIE (1951) Scotopic V'( ⁇ )).
- Table 2 shows the main initial characteristic values of the device 1 and the comparison device 2 at a current of 2 mA (current density of 50 mA / cm 2 ).
- the radiant flux and the external quantum efficiency were calculated using the radiance, assuming that the light distribution characteristics of the light emitting device were of the Lambersian type.
- the maximum peak wavelength of the emission spectrum of the device 1 is 801 nm
- the maximum peak wavelength of the emission spectrum of the comparison device 2 is 793 nm
- both devices are included in the light emitting layer 813 [Ir (Ir). It was found that it emits near-infrared light from dmdppbq) 2 (dpm)].
- the rising wavelength of the maximum peak on the short wavelength side was 754 nm.
- the rising wavelength of the maximum peak on the short wavelength side was 751 nm. It was found that in both the device 1 and the comparison device 2, the rising wavelength on the short wavelength side of the maximum peak is a sufficiently long wavelength.
- a relatively large emission peak (peak wavelength 523 nm) was confirmed in the wavelength range of visible light in the emission spectrum of the comparative device 2.
- the light emitted by the comparison device 2 includes light in a wavelength range having high luminosity among visible light. That is, the comparison device 2 can easily visually recognize the emission of visible light.
- the device 1 had a lower spectral radiance in the wavelength range of visible light than the comparative device 2.
- the maximum peak wavelength of the emission spectrum of the device 1 in the visible light wavelength region was 638 nm, and the emission spectrum of the device 1 had an emission peak in the wavelength region where the visual sensitivity was low even in the visible light. From this, it was found that the device 1 emits visible light in a wavelength region having low luminosity factor, and the emission intensity is low in the wavelength region of the visible light.
- the luminance / radiance of the device 1 (the value obtained by dividing the luminance value by the radiance value) is 0.05 cd ⁇ sr / W, and the luminance / radiance of the comparative device 2 is 2. It was 1 cd ⁇ sr / W. From this, it was found that the device 1 has an extremely low emission intensity of visible light with respect to the emission intensity of near infrared light. Therefore, it can be said that the device 1 is a light emitting device that emits near-infrared light and the light emission of visible light is difficult to see. On the other hand, in the comparison device 2, the emission intensity of visible light is higher than the emission intensity of near-infrared light, and it can be said that visible light is easily visible.
- the external quantum efficiency of device 1 was 2.5%. It can be said that this is a high value as the external quantum efficiency of a light emitting device that mainly emits near-infrared light because the emission intensity of visible light is weak.
- the external quantum efficiency of the device 1 was calculated from the measurement results using a near-infrared spectroradiometer (SR-NIR, manufactured by Topcon) in the wavelength range of 600 nm or more and 1030 nm or less.
- SR-NIR near-infrared spectroradiometer
- a mixed film A of the two host materials used for the device 1 and a mixed film B of the two host materials used for the comparison device 2 were prepared, and the emission spectrum (PL spectrum) was measured.
- 2.8 mDBtP2Bfqn and m-MTDATA are combinations that form an excited complex.
- 2mDBTBPDBq-II and PCBBiF are a combination that forms an excited complex.
- Table 3 shows the HOMO and LUMO levels of each host material.
- the HOMO level and LUMO level were derived from the electrochemical properties (reduction potential and oxidation potential) of the material measured by cyclic voltammetry (CV) measurement.
- Table 3 also shows the HOMO and LUMO levels of the guest materials used in the device 1 and the comparison device 2.
- the HOMO level and LUMO level of the two host materials used for the device 1 and the mixed film A will be described with reference to Table 3. It can be seen that the HOMO level of m-MTDATA is higher than the HOMO level of [Ir (dmdppbq) 2 (dpm)] and the HOMO level of 2.8 mDBtP2Bfqn, respectively. Specifically, the HOMO level (-4.98 eV) of m-MTDATA is 0.56 eV higher than the HOMO level (-5.54 eV) of [Ir (dmdppbq) 2 (dpm)].
- the difference between the HOMO level of m-MTDATA (-4.98 eV) and the LUMO level of 2.8 mDBtP2Bfqn (-3.31 eV) is 1.67 eV, which is [Ir (dmdppbq) 2 (dpm). )] Is smaller than the difference (2.05 eV) between the HOMO level (-5.54 eV) and the LUMO level (-3.49 eV).
- the HOMO level and the LUMO level of the two host materials used for the comparison device 2 and the mixed film B will be described with reference to Table 3. It can be seen that the HOMO level of PCBiF is higher than the HOMO level of [Ir (dmdppbq) 2 (dpm)] and the HOMO level of 2mDBTBPDBq-II, respectively. Specifically, the HOMO level (-5.36 eV) of PCBiF is 0.18 eV higher than the HOMO level (-5.54 eV) of [Ir (dmdppbq) 2 (dpm)].
- the difference between the HOMO level of PCBiF (-5.36 eV) and the LUMO level of 2 mDBTBPDBq-II (-2.94 eV) is 2.42 eV, [Ir (dmdppbq) 2 (dpm)]. This is larger than the difference (2.05 eV) between the HOMO level (-5.54 eV) and the LUMO level (-3.49 eV).
- the PL spectrum was measured at room temperature using a fluorometer (FS920 manufactured by Hamamatsu Photonics Co., Ltd.).
- FIGS. 8 and 9 show the PL spectrum of the mixed film A and the emission spectrum of the device 1 (similar to FIGS. 6 and 7). Note that FIG. 9 is different from FIG. 8 in that the vertical axis is a logarithmic display.
- FIG. 10 and 11 show the PL spectrum of the mixed film B and the emission spectrum of the comparison device 2 (similar to FIG. 6). Note that FIG. 11 is different from FIG. 10 in that the vertical axis is a logarithmic display.
- the maximum peak wavelength of the PL spectrum of the mixed film A was 678 nm. From the difference between the HOMO level of m-MTDATA and the LUMO level of 2.8 mDBtP2Bfqn, it can be said that the light emission of the mixed film A is derived from the excited complex formed by these two materials.
- the maximum peak wavelength of the PL spectrum of the mixed film B was 516 nm. From the difference between the HOMO level of PCBiF and the LUMO level of 2mDBTBPDBq-II, it can be said that the light emission of the mixed film B is derived from the excited complex formed by these two materials.
- the visible light emission confirmed by the comparison device 2 is an excitation formed by the two host materials. It was shown that the luminescence was derived from the complex.
- the maximum peak wavelength of the PL spectrum of the mixed film A is included in a wavelength region having low visibility. Therefore, the luminescence derived from the excited complex formed by the two host materials used for the mixed film A has low luminosity factor. Therefore, the device 1 is a light emitting device in which the light emission derived from the excited complex is hard to be visually recognized and the light emission of visible light is hard to be visually recognized.
- the HOMO level of m-MTDATA used for the mixed membrane A is 0.56 eV higher than the HOMO level of [Ir (dmdppbq) 2 (dpm)]. Further, the difference between the HOMO level of m-MTDATA and the LUMO level of 2.8 mDBtP2Bfqn is smaller than the difference between the HOMO level and LUMO level of [Ir (dmdppbq) 2 (dpm)]. .. As a result, the emission wavelength of the excitation complex formed by these two materials can be made longer, and the luminosity factor of the emission derived from the excitation complex can be lowered.
- step 1 Synthesis of 2,3-bis- (3,5-dimethylphenyl) -2-benzo [g] quinoxaline (abbreviation: Hdmdpbq)>
- Hdmdpbq was synthesized. 3.20 g of 3,3', 5,5'-tetramethylbenzyl, 1.97 g of 2,3-diaminonaphthalene, and 60 mL of ethanol were placed in a three-necked flask equipped with a reflux tube, and the inside was replaced with nitrogen, and then 90 ° C. Was stirred for 7 and a half hours. After a lapse of a predetermined time, the solvent was distilled off.
- step 1 The synthesis scheme of step 1 is shown in (a-1).
- step 2 15 mL of 2-ethoxyethanol, 5 mL of water, 1.81 g of Hdmdpbq obtained in step 1, and 0.66 g of iridium chloride hydrate (IrCl 3 ⁇ H 2 O) (manufactured by Furuya Metals Co., Ltd.) were added to an eggplant with a reflux tube. It was placed in a flask and the inside of the flask was replaced with argon. Then, it was irradiated with microwaves (2.45 GHz 100 W) for 2 hours to react. After a lapse of a predetermined time, the obtained residue was suction-filtered and washed with methanol to obtain the desired product (black solid, yield 1.76 g, yield 81%). The synthesis scheme of step 2 is shown in (a-2).
- the obtained residue was suction-filtered with methanol and then washed with water and methanol.
- the obtained solid was purified by silica gel column chromatography using dichloromethane as a developing solvent, and then recrystallized from a mixed solvent of dichloromethane and methanol to obtain the desired product (dark green solid, yield 0.42 g, 21% yield).
- 0.41 g of the obtained dark green solid was sublimated and purified by the train sublimation method. Under the sublimation purification conditions, the dark green solid was heated at 300 ° C. while flowing an argon gas at a pressure of 2.7 Pa and a flow rate of 10.5 mL / min. After sublimation purification, a dark green solid was obtained in a yield of 78%.
- the synthesis scheme of step 3 is shown in (a-3).
- the absorption spectrum was measured using an ultraviolet-visible spectrophotometer (V550 type manufactured by JASCO Corporation), a dichloromethane solution (0.010 mmol / L) was placed in a quartz cell, and the measurement was performed at room temperature.
- a fluorometer (FS920 manufactured by Hamamatsu Photonics Co., Ltd.) was used to measure the emission spectrum, and a dichloromethane deoxidizing solution (0.010 mmol / L) was placed in a quartz cell under a nitrogen atmosphere, sealed, and at room temperature. Measurements were made.
- the absorption spectrum shown in FIG. 12 shows the result of subtracting the absorption spectrum measured by putting only dichloromethane in the quartz cell from the absorption spectrum measured by putting the dichloromethane solution (0.010 mmol / L) in the quartz cell.
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Abstract
Description
図2Aは、発光装置の一例を示す上面図である。図2B、図2Cは、発光装置の一例を示す断面図である。
図3Aは、発光装置の一例を示す上面図である。図3Bは、発光装置の一例を示す断面図である。
図4A~図4Eは、電子機器の一例を示す図である。
図5は、実施例の発光デバイスを示す断面図である。
図6は、実施例の発光デバイスの発光スペクトルを示す図である。
図7は、実施例の発光デバイスの発光スペクトルを示す図である。
図8は、実施例の発光デバイス及び混合膜の発光スペクトルを示す図である。
図9は、実施例の発光デバイス及び混合膜の発光スペクトルを示す図である。
図10は、実施例の発光デバイス及び混合膜の発光スペクトルを示す図である。
図11は、実施例の発光デバイス及び混合膜の発光スペクトルを示す図である。
図12は、[Ir(dmdpbq)2(dpm)]の吸収スペクトルを示す図である。
図13は、[Ir(dmdpbq)2(dpm)]の発光スペクトルを示す図である。
本実施の形態では、本発明の一態様の発光デバイスについて図1を用いて説明する。
≪発光デバイスの基本的な構造≫
図1A~図1Cに、一対の電極間にEL層を有する発光デバイスの一例を示す。
次に、発光デバイスの具体的な構造及び作製方法について説明する。ここでは、図1Cに示すシングル構造を有する発光デバイスを用いて説明する。
第1の電極101及び第2の電極102を形成する材料としては、上述した両電極の機能が満たせるのであれば、以下に示す材料を適宜組み合わせて用いることができる。例えば、金属、合金、電気伝導性化合物、及びこれらの混合物などを適宜用いることができる。具体的には、In−Sn酸化物(ITOともいう)、In−Si−Sn酸化物(ITSOともいう)、In−Zn酸化物、In−W−Zn酸化物が挙げられる。その他、アルミニウム(Al)、チタン(Ti)、クロム(Cr)、マンガン(Mn)、鉄(Fe)、コバルト(Co)、ニッケル(Ni)、銅(Cu)、ガリウム(Ga)、亜鉛(Zn)、インジウム(In)、スズ(Sn)、モリブデン(Mo)、タンタル(Ta)、タングステン(W)、パラジウム(Pd)、金(Au)、白金(Pt)、銀(Ag)、イットリウム(Y)、ネオジム(Nd)などの金属、及びこれらを適宜組み合わせて含む合金を用いることもできる。その他、上記例示のない元素周期表の第1族または第2族に属する元素(例えば、リチウム(Li)、セシウム(Cs)、カルシウム(Ca)、ストロンチウム(Sr))、ユウロピウム(Eu)、イッテルビウム(Yb)などの希土類金属及びこれらを適宜組み合わせて含む合金、グラフェン等を用いることができる。
正孔注入層111は、陽極である第1の電極101からEL層103に正孔を注入する層であり、正孔注入性の高い材料を含む層である。
発光層113は、発光物質を含む層である。
電子輸送層114は、電子注入層115によって、第2の電極102から注入された電子を発光層113に輸送する層である。なお、電子輸送層114は、電子輸送性材料を含む層である。電子輸送層114に用いる電子輸送性材料は、1×10−6cm2/Vs以上の電子移動度を有する物質が好ましい。なお、正孔よりも電子の輸送性の高い物質であれば、これら以外のものも用いることができる。
電子注入層115は、電子注入性の高い物質を含む層である。電子注入層115には、フッ化リチウム(LiF)、フッ化セシウム(CsF)、フッ化カルシウム(CaF2)、リチウム酸化物(LiOx)等のようなアルカリ金属、アルカリ土類金属、またはそれらの化合物を用いることができる。また、フッ化エルビウム(ErF3)のような希土類金属化合物を用いることができる。また、電子注入層115にエレクトライドを用いてもよい。エレクトライドとしては、例えば、カルシウムとアルミニウムの混合酸化物に電子を高濃度添加した物質等が挙げられる。なお、上述した電子輸送層114を構成する物質を用いることもできる。
図1Bに示す発光デバイスにおいて、電荷発生層104は、第1の電極101(陽極)と第2の電極102(陰極)との間に電圧を印加したときに、EL層103aに電子を注入し、EL層103bに正孔を注入する機能を有する。
本実施の形態では、本発明の一態様の発光装置について図2及び図3を用いて説明する。
図2Aに発光装置の上面図を示し、図2B、図2Cに、図2Aの一点鎖線X1−Y1間及びX2−Y2間の断面図を示す。図2A~図2Cに示す発光装置は、例えば、照明装置に用いることができる。発光装置は、ボトムエミッション、トップエミッション、デュアルエミッションのいずれであってもよい。
本発明の一態様の発光装置は、パッシブマトリクス型またはアクティブマトリクス型とすることができる。アクティブマトリクス型の発光装置について図3を用いて説明する。
本実施の形態では、本発明の一態様の発光デバイスを用いることができる電子機器について図4を用いて説明する。
本実施例で示すデバイス1及び比較デバイス2は、図5に示すように、基板800上に第1の電極801が形成され、第1の電極801上に、EL層802として、正孔注入層811、正孔輸送層812、発光層813、電子輸送層814、及び電子注入層815が順次積層され、電子注入層815上に第2の電極803が積層された構造を有する。
デバイス1及び比較デバイス2の動作特性について測定した。なお、測定は室温(25℃に保たれた雰囲気)で行った。
上記実施例で用いたビス{4,6−ジメチル−2−[3−(3,5−ジメチルフェニル)−2−ベンゾ[g]キノキサリニル−κN]フェニル−κC}(2,2,6,6−テトラメチル−3,5−ヘプタンジオナト−κ2O,O’)イリジウム(III)(略称:[Ir(dmdpbq)2(dpm)])の合成方法について、具体的に説明する。[Ir(dmdpbq)2(dpm)]の構造を以下に示す。
まず、ステップ1では、Hdmdpbqを合成した。3,3’,5,5’−テトラメチルベンジル3.20g、2,3−ジアミノナフタレン1.97g、エタノール60mLを、還流管を付けた三口フラスコに入れ、内部を窒素置換した後、90℃で7時間半撹拌した。所定時間経過後、溶媒を留去した。その後、トルエンを展開溶媒とするシリカゲルカラムクロマトグラフィーで精製し、目的物を得た(黄色固体、収量3.73g、収率79%)。ステップ1の合成スキームを(a−1)に示す。
1H−NMR.δ(CD2Cl2):2.28(s,12H),7.01(s,2H),7.16(s,4H),7.56−7.58(m,2H),8.11−8.13(m,2H),8.74(s,2H).
次に、ステップ2では、[Ir(dmdpbq)2Cl]2を合成した。2−エトキシエタノール15mL、水5mL、ステップ1で得たHdmdpbq1.81g、及び、塩化イリジウム水和物(IrCl3・H2O)(フルヤ金属社製)0.66gを、還流管を付けたナスフラスコに入れ、フラスコ内をアルゴン置換した。その後、マイクロ波(2.45GHz 100W)を2時間照射し、反応させた。所定時間経過後、得られた残渣をメタノールで吸引ろ過、洗浄し、目的物を得た(黒色固体、収量1.76g、収率81%)。ステップ2の合成スキームを(a−2)に示す。
そして、ステップ3では、[Ir(dmdpbq)2(dpm)]を合成した。2−エトキシエタノール20mL、ステップ2で得た[Ir(dmdpbq)2Cl]21.75g、ジピバロイルメタン(略称:Hdpm)0.50g、及び、炭酸ナトリウム0.95gを、還流管を付けたナスフラスコに入れ、フラスコ内をアルゴン置換した。その後、マイクロ波(2.45GHz 100W)を3時間照射した。得られた残渣を、メタノールで吸引ろ過した後、水、メタノールで洗浄した。得られた固体を、ジクロロメタンを展開溶媒とするシリカゲルカラムクロマトグラフィーにより精製した後、ジクロロメタンとメタノールの混合溶媒にて再結晶することにより、目的物を得た(暗緑色固体、収量0.42g、収率21%)。得られた暗緑色固体0.41gを、トレインサブリメーション法により昇華精製した。昇華精製条件は、圧力2.7Pa、アルゴンガスを流量10.5mL/minで流しながら、300℃で暗緑色固体を加熱した。昇華精製後、暗緑色固体を収率78%で得た。ステップ3の合成スキームを(a−3)に示す。
Claims (20)
- 発光層を有する発光デバイスであり、
前記発光層は、発光性の有機化合物及びホスト材料を有し、
前記発光デバイスの発光スペクトルの最大ピーク波長は、750nm以上900nm以下であり、
輝度A[cd/m2]と、放射輝度B[W/sr/m2]とは、0≦A/B≦1[cd・sr/W]を満たす、発光デバイス。 - 請求項1において、
前記ホスト材料におけるHOMO準位とLUMO準位との差は、1.35eV以上2.25eV以下である、発光デバイス。 - 請求項1において、
前記ホスト材料は、第1の有機化合物及び第2の有機化合物を有し、
前記第1の有機化合物のHOMO準位は、前記第2の有機化合物のHOMO準位よりも高く、
前記第1の有機化合物のHOMO準位と前記第2の有機化合物のLUMO準位との差は、前記発光性の有機化合物のHOMO準位とLUMO準位との差に比べて小さい、発光デバイス。 - 請求項3において、
前記第1の有機化合物と前記第2の有機化合物とは、励起錯体を形成する物質である、発光デバイス。 - 請求項3または4において、
前記第1の有機化合物のHOMO準位と前記第2の有機化合物のLUMO準位との差は、1.35eV以上2.25eV以下である、発光デバイス。 - 発光層を有する発光デバイスであり、
前記発光層は、発光性の有機化合物及びホスト材料を有し、
前記発光デバイスの発光スペクトルの最大ピーク波長は、750nm以上900nm以下であり、
前記ホスト材料のHOMO準位は、前記発光性の有機化合物のHOMO準位よりも0.4eV以上高く、
前記ホスト材料のHOMO準位とLUMO準位との差は、前記発光性の有機化合物のHOMO準位とLUMO準位との差に比べて小さい、発光デバイス。 - 請求項6において、
前記ホスト材料におけるHOMO準位とLUMO準位との差は、1.35eV以上2.25eV以下である、発光デバイス。 - 発光層を有する発光デバイスであり、
前記発光層は、発光性の有機化合物及びホスト材料を有し、
前記発光デバイスの発光スペクトルの最大ピーク波長は、750nm以上900nm以下であり、
前記ホスト材料は、第1の有機化合物及び第2の有機化合物を有し、
前記第1の有機化合物のHOMO準位は、前記発光性の有機化合物のHOMO準位よりも0.4eV以上高く、
前記第1の有機化合物のHOMO準位は、前記第2の有機化合物のHOMO準位よりも高く、
前記第1の有機化合物のHOMO準位と前記第2の有機化合物のLUMO準位との差は、前記発光性の有機化合物のHOMO準位とLUMO準位との差に比べて小さい、発光デバイス。 - 請求項8において、
前記第1の有機化合物と前記第2の有機化合物とは、励起錯体を形成する物質である、発光デバイス。 - 請求項8または9において、
前記第1の有機化合物のHOMO準位と前記第2の有機化合物のLUMO準位との差は、1.35eV以上2.25eV以下である、発光デバイス。 - 請求項1乃至10のいずれか一において、
前記発光スペクトルにおける最大ピークの短波長側の立ち上がり波長は、650nm以上である、発光デバイス。 - 請求項1乃至11のいずれか一において、
前記発光性の有機化合物は、溶液における発光スペクトルの、最大ピークの短波長側の立ち上がり波長が650nm以上である、発光デバイス。 - 請求項1乃至12のいずれか一において、
外部量子効率は、1%以上である、発光デバイス。 - 請求項1乃至13のいずれか一において、
前記発光性の有機化合物は、金属−炭素結合を有する有機金属錯体である、発光デバイス。 - 請求項14において、
前記有機金属錯体は、2環以上5環以下の縮合複素芳香環を有し、
前記縮合複素芳香環は、前記金属に配位している、発光デバイス。 - 請求項1乃至15のいずれか一において、
前記発光性の有機化合物は、シクロメタル錯体である、発光デバイス。 - 請求項1乃至16のいずれか一に記載の発光デバイスと、
トランジスタ及び基板の一方または双方と、を有する、発光装置。 - 請求項17に記載の発光装置と、
コネクタ及び集積回路の一方または双方と、を有する、発光モジュール。 - 請求項18に記載の発光モジュールと、
アンテナ、バッテリ、筐体、カメラ、スピーカ、マイク、及び操作ボタンのうち少なくとも一つと、を有する、電子機器。 - 請求項17に記載の発光装置と、
筐体、カバー、及び支持台のうち少なくとも一つと、を有する、照明装置。
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