CN114551744A - Light emitting layer, organic electroluminescent device including the same, and display apparatus - Google Patents

Light emitting layer, organic electroluminescent device including the same, and display apparatus Download PDF

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CN114551744A
CN114551744A CN202210182947.3A CN202210182947A CN114551744A CN 114551744 A CN114551744 A CN 114551744A CN 202210182947 A CN202210182947 A CN 202210182947A CN 114551744 A CN114551744 A CN 114551744A
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light
layer
emitting layer
tadf
quenching
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刘统治
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BOE Technology Group Co Ltd
Chengdu BOE Optoelectronics Technology Co Ltd
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Chengdu BOE Optoelectronics Technology Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/625—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing at least one aromatic ring having 7 or more carbon atoms, e.g. azulene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Electroluminescent Light Sources (AREA)

Abstract

The invention discloses a luminescent layer, which comprises a luminescent layer main body and a quenching layer positioned in the luminescent layer main body; wherein, still have exciton recombination center in the luminescent layer host body, and the distance between quenching layer and exciton recombination center is greater than Forster energy transfer radius. The quenching layer introduced into the luminescent layer and having the distance between the quenching layer and the exciton recombination center larger than the Forster energy transfer radius can well quench the triplet excitons with long service life, and the service life of the TADF-OLED is improved. The invention also discloses an organic electroluminescent device and a display device comprising the luminescent layer.

Description

Light emitting layer, organic electroluminescent device including the same, and display apparatus
Technical Field
The invention relates to the technical field of display. And more particularly, to a light emitting layer, an organic electroluminescent device including the same, and a display apparatus.
Background
TADF materials enable RISC of triplet excitons, up-converting 75% of triplet excitons to singlet excitons, and thus internal quantum efficiencies of 100% can be achieved for OLEDs based on TADF emitters. However, TADF emitters contain long-lived (microsecond-scale) triplet excitons, and longer exciton lifetimes increase triplet exciton density in the light-emitting layer, leading to exciton-to-exciton collisions, exacerbating the TTA/TPA effect, resulting in decreased stability of the light-emitting layer, and decreasing OLED lifetime. Under the influence of the carrier transport capability of the device functional layer, the light emitting layer in the OLED generally has a narrow exciton recombination center, and light emission mainly comes from the exciton recombination center. Here, short-lived triplet excitons undergo RISC, up-conversion to singlet excitons emits light, while long-lived triplet excitons diffuse into the region of the light-emitting layer remote from the exciton recombination center and undergo TTA/TPA.
Disclosure of Invention
Based on the above facts, the present invention provides a light emitting layer, an organic electroluminescent device and a display device including the light emitting layer, so as to at least partially solve the problem that in the current TADF-OLED device, the long-life triplet excitons brought by the TADF emitter increase the triplet exciton density in the light emitting layer, aggravate the TTA/TPA effect, and reduce the lifetime of the OLED.
In one aspect, the present invention provides a light emitting layer comprising a light emitting layer host and a quenching layer located within the light emitting layer host; wherein, still have exciton recombination center in the luminescent layer host body, and the distance between quenching layer and exciton recombination center is greater than Forster energy transfer radius.
Optionally, the exciton recombination center is spaced from the quenching layer by a distance greater than 10 nm.
Optionally, the luminescent layer body is formed by mixing a host material and a TADF luminescent material.
Optionally, the quenching layer is formed of a light emitting layer host and a quencher doped therein.
Optionally, the overlap area between the absorption spectrum of the quencher and the emission spectrum of the TADF luminescent material is above 10%.
Alternatively, the S1 and T1 energy levels of the host material are both greater than the S1 and T1 energy levels of the TADF luminescent material, the difference between the S1 and T1 energy levels of the TADF luminescent material is less than 0.3eV, the difference between the S1 energy level of the TADF luminescent material and the S1 energy level of the quencher is less than 0.1eV, and the T1 energy level of the TADF luminescent material is greater than the T1 energy level of the quencher.
Optionally, the mass of the TADF luminescent material accounts for 30% or less of the total mass of the host material and the TADF luminescent material, and the mass of the quencher accounts for 2% or less of the total mass of the host material and the TADF luminescent material.
Optionally, the thickness of the light emitting layer is 30-40nm, and the thickness of the quenching layer is 2-4 nm.
In a further aspect, the present invention provides an organic electroluminescent device comprising a light-emitting layer as described above.
In a further aspect, the present invention provides a display apparatus comprising an organic electroluminescent device as described above.
The invention has the following beneficial effects:
in the luminescent layer provided by the invention, the quenching layer which is introduced and has the distance with the exciton recombination center larger than the Forster energy transfer radius can well quench the triplet exciton with long service life, thereby improving the service life of the TADF-OLED.
The organic electroluminescent device and the display device provided by the invention contain the luminescent layer, so that the organic electroluminescent device and the display device have the beneficial effects brought by the luminescent layer, and are not repeated herein.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 shows a schematic structure of a light-emitting layer in an embodiment of the present invention.
Fig. 2 shows a schematic energy transfer diagram of a light emitting layer in an embodiment of the present invention.
Fig. 3 shows a schematic structural diagram of an organic electroluminescent device in an embodiment of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
In this embodiment, some terms used represent that:
d: a donor; a: a receptor; TADF: thermally activated delayed fluorescence; an OLED: an organic light emitting diode; RISC: reverse intersystem crossing; ISC: inter-system jump; TTA: triplet-triplet exciton annihilation; TPA: triplet exciton-polaron annihilation.
Aiming at the problems that in the existing TADF-OLED device, the density of triplet excitons in a light-emitting layer is increased by long-life triplet excitons brought by a TADF emitter, the TTA/TPA effect is aggravated and the service life of the OLED is reduced, the inventors of the invention try to start from molecular design, increase the torsion angle of a TADF molecule D-A and reduce Delta E in order to reduce the triplet exciton life and the exciton density of the TADF emitterSTThe RISC of triplet excitons is promoted, but at the same time the oscillator intensity is reduced, reducing PLQY, resulting in a reduction in the EQE of the OLED. The super-fluorescent device utilizes Forster energy transfer from a sensitizing agent to a fluorescent emitter to separate an exciton recombination region from a luminescence center, so that exciton density and exciton service life in a luminescent layer are reduced, but the Dexter energy transfer from a main body and the sensitizing agent to the fluorescent emitter exists, so that partial energy loss is caused, and the OLED efficiency is reduced.
In this example, it was found that, in the case of the TADF-OLED, by doping the fluorescent material with energy matching at a specific distance from the exciton recombination center of the light-emitting layer to form a quenching layer, the long-life excitons diffused from the exciton recombination center can be quenched, while the short-life excitons are not adversely affected and the light emission efficiency thereof is maintained. The density of triplet excitons in the light-emitting layer is reduced, the TTA/TPA effect is inhibited, the stability of the light-emitting layer is increased, and the service life of the OLED can be prolonged. Based on this, the embodiment of the present invention provides a light emitting layer, as shown in fig. 1, including a light emitting layer host 2 and a quenching layer 1 located in the light emitting layer host 2; wherein, the luminescent layer main body 2 is also provided with an exciton recombination center 3, and the distance between the exciton recombination center 3 and the quenching layer 1 is larger than the Forster energy transfer radius.
In the technical scheme, the distance between the quenching layer 1 and the exciton recombination center 3 region is larger than the Forster energy transfer radius, so that the radiation luminescence of the exciton recombination center 3 region cannot be influenced. The long-life excitons diffuse out of the exciton recombination center 3 region, the singlet-state excitons and the triplet-state excitons can be mutually converted in the diffusion process, Forster energy transfer preferentially occurs when the distance between the quenching layer and the quenching layer meets the Forster energy transfer radius, and the quenching layer consumes the long-life singlet-state excitons and triplet-state excitons in the light-emitting layer; when Dexter energy transfer occurs when excitons that diffuse farther away are spaced from the quenching layer to meet the Dexter energy transfer radius, the quenching layer directly consumes long-lived triplet excitons in the light-emitting layer. In some embodiments, the distance between the exciton recombination center 3 and the quenching layer 1 is greater than 10 nm.
In this embodiment, the exciton recombination center 3 is located at the side of the light-emitting layer close to the hole blocking layer.
In this embodiment, the light-emitting layer host 2 is formed by mixing a host material and a TADF light-emitting material (guest material). Host materials suitable for use in this embodiment include, but are not limited to, red host materials, blue host materials, green host materials (e.g., mCP, CBP, DPEPO, etc.) as are conventionally used in the art.
In some embodiments, the quenching layer 1 is formed of a light emitting layer host 2 and a quencher doped therein. That is, the quenching layer 1 is formed by doping a quenching agent in a partial region of the light-emitting layer host 2. Suitable quenchers may be fluorescent materials.
In some embodiments, the overlap area between the absorption spectrum of the quencher and the emission spectrum of the TADF luminescent material is above 10%. The larger the overlapping area of the two is, the more favorable the energy transfer is.
In some embodiments, the S1 and T1 energy levels of the host material are both greater than the S1 and T1 energy levels of the TADF light emitting material, the difference between the S1 and T1 energy levels of the TADF light emitting material is less than 0.3eV, the difference between the S1 energy level of the TADF light emitting material and the S1 energy level of the quencher is less than 0.1eV, and the T1 energy level of the TADF light emitting material is greater than the T1 energy level of the quencher. Wherein the S1 and T1 energy levels of the host material are both greater than the S1 and T1 energy levels of the TADF luminescent material. The energy of the host is transferred to the TADF material of the object, so that the object can emit light; the difference between the S1 and T1 energy levels of the TADF luminescent material is less than 0.3 eV. RISC is generated by the TADF material to generate delayed fluorescence; the difference between the S1 energy level of the TADF luminescent material and the S1 energy level of the quencher is less than 0.1eV, and the T1 energy level of the TADF luminescent material is greater than the T1 energy level of the quencher. Facilitating the transfer of excess energy in the TADF material to the quencher.
In some embodiments, the TADF phosphor comprises less than 30% by mass of the total mass of the host material and the TADF phosphor, and the quencher comprises less than 2% by mass of the total mass of the host material and the TADF phosphor. The TADF guest luminescent material with high concentration can cause concentration quenching before luminescent molecules and reduce the luminous efficiency, and the proportion of the TADF guest luminescent material is more suitable to be less than 30 wt%; similarly, if the concentration of the quencher is too high, the emission intensity of the quencher is greatly increased, which affects the light emission effect of the device.
In some embodiments, in this embodiment, the thickness of the light-emitting layer is 30 to 40nm and the thickness of the quenching layer 1 is 2 to 4 nm.
Fig. 2 shows a schematic energy transfer diagram of the light-emitting layer of the present embodiment in use. Wherein, the process of energy transfer is as follows: the holes and electrons combine on the host material to generate S1, T1 excitons, followed by energy transfer to the guest material, which generates S1, T1 excitons in the guest material. The guest is a TADF material, and the T1 exciton is converted to S1 exciton by RISC to radiate fluorescence. Meanwhile, a small part of S1/T1 excitons in the guest luminescent molecule diffuse outwards and transfer energy to the quenching material when diffusing to the quenching material, and the quenching material consumes the energy through a radiation or non-radiation process.
Yet another embodiment of the present invention provides an organic electroluminescent device, as shown in fig. 3, which includes an anode 301, a hole injection layer 302, a hole transport layer 303, an electron blocking layer 304, a light emitting layer 305 as described in the above embodiments, a hole blocking layer 306, an electron transport layer 307, an electron injection layer 308, and a cathode 309, which are sequentially disposed.
Yet another embodiment of the present invention provides a display apparatus including the organic electroluminescent device as described above.
The technical solution of the present invention is described below with reference to some specific examples:
the materials used in the present embodiment are commercially available unless otherwise specified.
In each of examples and comparative examples, the structure of the organic electroluminescent device is shown in fig. 3, and in each of the following examples and comparative examples, the structure of the organic electroluminescent device is not the same except for the structure of the light emitting layer, and the remaining film layers are uniform. The specific device structure is shown in fig. 3, wherein 301 is an ITO anode, and on the surface of which a hole injection layer TAPC (thickness 30nm), a hole transport layer TCTA (thickness 15nm) 303, an electron blocking layer mCP (thickness 10nm) 304, a light emitting layer (thickness 30nm) 305, a hole blocking layer DPEPO (thickness 5nm) 306, an electron transport layer TmPyPb (thickness 45nm), an electron injection layer LiF (thickness 1nm) 308, and a cathode layer Al 309 are sequentially evaporated.
The light emitting layer structures of several comparative examples and examples are as follows, the light emitting layer material structures are as follows,
comparative example 1: 80 wt% mCP 20 wt% 4CzIPN (30 nm).
Comparative example 2: 80 wt% mCP 20 wt% 4CzIPN (22nm)/80 wt% mCP 20 wt% 4CzIPN 1 wt% TAD (3nm)/80 wt% mCP 20 wt% 4CzIPN (5 nm).
Comparative example 3: 80 wt% mCP 20 wt% 4CzIPN (18nm)/80 wt% mCP 20 wt% 4CzIPN 1 wt% TAD (3nm)/80 wt% mCP 20 wt% 4CzIPN (9 nm).
Comparative example 4: 80 wt% mCP 20 wt% 4CzIPN (14nm)/80 wt% mCP 20 wt% 4CzIPN 1 wt% TAD (3nm)/80 wt% mCP 20 wt% 4CzIPN (13 nm).
Comparative example 5: 80 wt% mCP 20 wt% 4CzIPN (10nm)/80 wt% mCP 20 wt% 4CzIPN 1 wt% TAD (3nm)/80 wt% mCP 20 wt% 4CzIPN (17 nm).
Example 1: 80 wt% mCP 20 wt% 4CzIPN (6nm)/80 wt% mCP 20 wt% 4CzIPN 1 wt% TAD (3nm)/80 wt% mCP 20 wt% 4CzIPN (21 nm).
Example 2: 80 wt% mCP 20 wt% 4CzIPN (2nm)/80 wt% mCP 20 wt% 4CzIPN 1 wt% TAD (3nm)/80 wt% mCP 20 wt% 4CzIPN (25 nm).
In comparative example 1, the entire light-emitting layer is formed by mixing a host material and a guest material TADF; in comparative example 2 to example 2, the above compositions correspond to the compositions A/B/C in FIG. 1, respectively. Further exemplifying: in the light-emitting layer of comparative example 2, the composition of the segment A was 80 wt% mCP:20 wt% 4CzIPN, with a thickness of 22 nm; the composition of the section B is 80 wt% mCP, 20 wt% 4CzIPN, 1 wt% TAD and the thickness is 3 nm; the composition of the C section is 80 wt% mCP and 20 wt% 4CzIPN, and the thickness is 5 nm.
In the above examples and comparative examples, the Forster energy transfer radius is theoretically 10nm or less. Since the thickness of the luminescent layer is 30nm, the area of the exciton recombination center 3 in the luminescent layer is close to one side of the hole blocking layer and is similar in position. The exciton recombination center was tested and found to be approximately 6nm to 10nm near the right (near the hole blocking layer). Therefore, when the quenching layer 1 is disposed close to the electron blocking layer, fig. 1 shows that the farther away from the exciton recombination center 3 region (labeled 1), the smaller the direct influence of the quenching layer on the exciton recombination center 3 region, and the efficiency and the lifetime of the corresponding device are gradually improved. Tests have found that the exciton recombination centers 3 are located approximately 6nm from the EML/HBL interface, distance E, and the exciton recombination centers 3 have a thickness of 4nm, distance D.
Wherein, the chemical formulas of mCP, 4CzIPN and TAD are as follows:
Figure BDA0003521849060000051
and packaging the devices of the comparative examples 1-5 and the examples 1-2 by adopting ultraviolet curing resin after completing the evaporation of each layer. Testing electroluminescent performance of the packaged device by adopting IVL (in-line voltage) testing equipment under the conditions of current density of 15mA/cm2The test items include current efficiency (CE @15 mA/cm)2) Power efficiency (PE @15 mA/cm)2) External quantum efficiency (EQE @15 mA/cm)2) Color coordinates CIE (x, y) @15mA/cm2Testing the service life of a device by using life time equipment under the test condition of T90@15mA/cm2The specific parameters are shown in table 1.
TABLE 1 comparative examples 1-5 and examples 1-2 device parameters
Figure BDA0003521849060000052
Since the host material mCP is P-type host, the exciton recombination center in the light-emitting layer is positioned close to HBL, and for comparative examples 2 and 3, the quenching layer and the exciton recombination center region are overlapped, so that the energy transfer from 4CzIPN to TAD Dexter is promoted, the serious loss of efficiency is caused, and the decline of EQE and CE is obvious. For comparative examples 4 and 5, the quenching layer is separated from the exciton recombination central region, but the spacing is smaller than the Forster energy transfer radius, part of the short-lifetime excitons which induce the exciton recombination central region and are originally used for radiation luminescence are transferred to TAD through Forster or Dexter energy, partial energy loss is caused, EQE and CE are reduced, but the long-lifetime excitons which are diffused out of the partial exciton recombination central region are quenched at the same time, TTA/TPA is slightly inhibited, and the working life of the device is improved. For examples 1 and 2, the quenching layer is separated from the exciton recombination center region, and the distance is larger than the Forster energy transfer radius, so that short-life excitons of the exciton recombination center region due to radiation luminescence are not affected, the original higher EQE and CE are maintained, meanwhile, the long-life excitons diffused from the exciton recombination center region are quenched, the TTA/TPA is effectively inhibited, and the service life of the device is further prolonged.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (10)

1. A light-emitting layer is characterized in that the light-emitting layer comprises a light-emitting layer main body and a quenching layer positioned in the light-emitting layer main body; wherein, still have exciton recombination center in the luminescent layer host body, and the distance between quenching layer and exciton recombination center is greater than Forster energy transfer radius.
2. The light-emitting layer of claim 1, wherein the exciton recombination center is separated from the quenching layer by a distance greater than 10 nm.
3. The luminescent layer of claim 1, wherein the luminescent layer body is formed by mixing a host material with a TADF luminescent material.
4. The light-emitting layer according to claim 3, wherein the quenching layer is formed of a light-emitting layer host and a quencher doped therein.
5. The light-emitting layer according to claim 4, wherein the overlapping area between the absorption spectrum of the quencher and the emission spectrum of the TADF light-emitting material is 10% or more.
6. The light-emitting layer of claim 4, wherein the S1 and T1 energy levels of the host material are both greater than the S1 and T1 energy levels of the TADF light-emitting material, the difference between the S1 and T1 energy levels of the TADF light-emitting material is less than 0.3eV, the difference between the S1 energy level of the TADF light-emitting material and the S1 energy level of the quencher is less than 0.1eV, and the T1 energy level of the TADF light-emitting material is greater than the T1 energy level of the quencher.
7. The luminescent layer according to claim 4, wherein the TADF luminescent material accounts for less than 30% of the total mass of the host material and the TADF luminescent material, and the quencher accounts for less than 2% of the total mass of the host material and the TADF luminescent material.
8. The light-emitting layer according to claim 1, wherein the light-emitting layer has a thickness of 30 to 40nm and the quenching layer has a thickness of 2 to 4 nm.
9. An organic electroluminescent device comprising the light-emitting layer according to any one of claims 1 to 8.
10. A display device comprising the organic electroluminescent device according to claim 9.
CN202210182947.3A 2022-02-25 2022-02-25 Light emitting layer, organic electroluminescent device including the same, and display apparatus Pending CN114551744A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024000654A1 (en) * 2022-06-28 2024-01-04 武汉华星光电半导体显示技术有限公司 Oled device and display apparatus

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024000654A1 (en) * 2022-06-28 2024-01-04 武汉华星光电半导体显示技术有限公司 Oled device and display apparatus

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