CN109449303B - OLED device - Google Patents
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- CN109449303B CN109449303B CN201811311387.7A CN201811311387A CN109449303B CN 109449303 B CN109449303 B CN 109449303B CN 201811311387 A CN201811311387 A CN 201811311387A CN 109449303 B CN109449303 B CN 109449303B
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
- H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
- H10K50/131—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit with spacer layers between the electroluminescent layers
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Abstract
The application discloses an OLED device which comprises a first electrode, an organic functional layer and a reflecting electrode which are sequentially arranged; the organic functional layer comprises at least one infrared light-emitting layer and at least one heat-activated delayed fluorescent material light-emitting layer. This application is through infrared OLED luminescent material and phosphorescence, fluorescent material or thermal activation delay fluorescent material's combination, and the infrared ray that utilizes infrared luminescent layer to send can heat other functional material, improves organic functional material's carrier mobility under the low temperature environment, alleviates the phenomenon that the device voltage rose to improve the stability of device under the low temperature, reduce operating voltage. In addition, the thermal activation delayed fluorescent material is heated by infrared rays emitted by the infrared light emitting layer, so that more triplet excitons in the thermal activation delayed fluorescent material are converted into singlet excitons through reverse intersystem crossing to emit light, and the light emitting efficiency is improved.
Description
Technical Field
The application belongs to the technical field of organic electroluminescence, and particularly relates to an OLED device.
Background
OLED (Organic Light Emitting Diode, chinese name Organic Light Emitting display) refers to a phenomenon in which an Organic semiconductor material and a Light Emitting material emit Light by carrier injection and recombination under electric field driving. A display or an illumination product manufactured according to such a light emitting principle is called an organic light emitting display or an organic light emitting illumination product.
OLED (organic light emitting diode) is a new generation of display and lighting technology, and currently shows great development potential, and currently, the improvement of efficiency and lifetime of OLED is still the current key as lighting technology.
The OLED material system is generally divided into a fluorescent material, a phosphorescent material and a thermally activated delayed fluorescent material, the fluorescent material has low cost but low efficiency, and the phosphorescent material has high efficiency but high cost, and the thermally activated delayed fluorescent material called as the next generation organic light emitting material theoretically has the characteristics of high efficiency and low cost. However, the thermally activated delayed fluorescent material has a better effect at a higher temperature, and meanwhile, in the aspect of reliability, the current OLED device has the problem of high voltage rise due to the reduction of carrier mobility at a low temperature.
Disclosure of Invention
In view of the above-mentioned drawbacks and deficiencies of the prior art, it is desirable to provide an OLED device to alleviate the voltage rise phenomenon of the OLED device at low temperatures and to improve the device efficiency.
The application provides an OLED device, which comprises a first electrode, an organic functional layer and a reflecting electrode which are sequentially arranged; the organic functional layer comprises an infrared light-emitting layer and a heat-activated delayed fluorescent material light-emitting layer. This application can cooperate other phosphorescence, fluorescent material again through the combination of infrared OLED luminescent material and TADF material (thermal activation delays fluorescent material), and the infrared ray that utilizes infrared luminescent layer to send can heat other functional material, improves the carrier mobility of organic functional material under the low temperature environment, alleviates the phenomenon that the device voltage rose at low temperature to improve the stability of device under the low temperature, reduce operating voltage. In addition, the thermal activation delayed fluorescent material is heated by infrared rays emitted by the infrared light emitting layer, more triplet excitons in the thermal activation delayed fluorescent material are promoted to be converted into singlet excitons through reverse intersystem crossing (RIST) to emit light, and therefore the light emitting efficiency is improved.
Preferably, the distance from the infrared light emitting layer to the reflective electrode is set to k λ/4n, where k is an integral multiple of 2, where λ is a dominant wavelength of light emission of the infrared light emitting layer (i.e., a wavelength corresponding to a peak position), and n is a refractive index of the organic functional layer. The design makes the infrared ray in the state of destructive interference inside the device, and the infrared ray is limited inside the device, so that the normal light emission of the device is not influenced.
Preferably, the infrared light-emitting layer emits light in a dominant wavelength range of 700nm to 2500 nm.
Preferably, the infrared light-emitting layer material is an organic small molecule material, an organic polymer, a rare earth complex, a transition metal complex, a quantum dot, an organic/hybrid perovskite material, or the like.
Preferably, the OLED device structure is a single-layer or stacked-layer structure.
Preferably, the organic functional layer further comprises a visible light fluorescent light emitting layer and/or a visible light phosphorescent light emitting layer.
The application has the advantages and positive effects that: the infrared OLED material can emit infrared rays, and TADF is used as a thermal delay fluorescent material and has excellent high-temperature resistance, and the luminous efficiency is higher even at high temperature. The application provides a new OLED device structure, through the combination of infrared OLED luminescent material and phosphorescence, fluorescent material or TADF material, can alleviate the phenomenon that the device voltage rose at low temperature, and can also improve the luminous efficiency of TADF material with TADF material collocation.
Meanwhile, the influence of the introduction of the infrared light emitting layer on the light emitting performance of the device can be reduced by reasonably selecting the distance between the infrared light emitting layer and the reflecting electrode.
Meanwhile, the material of the infrared luminescent layer is reasonably selected, so that the main luminescent wavelength range is 700nm-2500nm, the range can ensure the effect of heating TADF to improve the efficiency, and the heating temperature does not damage other organic luminescent layer materials.
In addition to the technical problems addressed by the present application, the technical features constituting the technical solutions, and the advantages brought by the technical features of the technical solutions described above, other technical problems solved by the present application, other technical features included in the technical solutions, and advantages brought by the technical features will be further described in detail below with reference to the accompanying drawings.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, made with reference to the accompanying drawings in which:
fig. 1 is a schematic structural diagram of an OLED device provided in embodiments 1, 2 and 4 of the present application;
FIG. 2 is a schematic structural diagram of an OLED device provided in example 3 of the present application;
FIG. 3 is a schematic structural diagram of an OLED device provided in comparative example 1 of the present application.
Fig. 4 is a schematic structural diagram of the OLED devices provided in comparative examples 2 and 3 of the present application.
In the figure: 1. a first electrode; 2. an organic functional layer; 21. a light emitting layer; 22. a CGL charge generation layer; 3. and a reflective electrode.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention. It should be noted that, for convenience of description, only the portions related to the present invention are shown in the drawings.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments with reference to the attached drawings.
Example 1
Referring to fig. 1, the present embodiment provides an OLED device, which includes a first electrode 1, an organic functional layer 2, and a reflective electrode 3 sequentially disposed. The device structure of the embodiment is a three-layer stacked device, the organic functional layer 2 has 3 independent light emitting layers 21, and a CGL charge generation layer 22 is disposed between the adjacent light emitting layers 21. The organic functional layer comprises 3 different light emitting layers from a first electrode 1 to a reflecting electrode 3, namely a blue light emitting layer with the light emitting wavelength of 470nm, an orange light emitting layer with the light emitting wavelength of 560nm and an infrared light emitting layer with the light emitting dominant wavelength of 780nm in sequence, wherein the light emitting layer with the light emitting wavelength of 470nm adopts a thermal activation delayed fluorescence material DMOC-DPS, the light emitting layer with the light emitting wavelength of 560nm adopts a phosphorescence material m-PF-py, and the infrared light emitting layer with the light emitting wavelength of 780nm adopts Ir (mpbqx-g)2acac。
The device provided by the embodiment is 12.6V when operated at a low temperature (-40 ℃) with fixed output brightness, and after 5 minutes of operation, the voltage is reduced to 11.3V under the same brightness, so that the operation characteristic of the device at the low temperature is effectively improved. And under the infrared irradiation, more triplet excitons in the thermal activation delayed fluorescent material are promoted to be converted into singlet excitons to emit light through reverse intersystem crossing, so that the luminous efficiency is improved, and the maximum external quantum efficiency of the device reaches 37%.
The specific device structure is as follows:
ITO/NPB(10nm)/DPEPO(20nm)：DMOC-DPS 10％/Bphen(10nm)/Bphen(20nm)：Mg 5％)/MoO3(10nm)/NPB(10nm)/TCTA(20nm)/mcp(30nm)：m-PF-py 12％/Bphen(30nm)Bphen(20nm)：Mg 5％)/MoO3(10nm)/NPB(10nm)/TCTA(20nm)/mcp(30nm)：Ir(mpbqx-g)2acac4％/Bphen(30nm)/LiF(1nm)/Al(150nm)
wherein m-PF-py has the following structural formula:
Ir(mpbqx-g)2the acac structural formula is as follows:
the embodiment also provides a lighting device comprising the OLED device.
Example 2
Referring to fig. 1, the present embodiment provides an OLED device, which includes a first electrode 1, an organic functional layer 2, and a reflective electrode 3 sequentially disposed. The device structure of the embodiment is a three-layer stacked device, the organic functional layer 2 has 3 independent light emitting layers 21, and a CGL charge generation layer 22 is disposed between the adjacent light emitting layers 21. 3 different light emitting layers in the organic functional layer comprise an infrared light emitting layer with the main light emitting wavelength of 780nm, a blue light emitting layer with the light emitting wavelength of 470nm and an orange light emitting layer with the light emitting wavelength of 560nm from the first electrode 1 to the reflecting electrode 3 in sequence, wherein the light emitting layer with the light emitting wavelength of 470nm adopts a thermal activation delayed fluorescence material DMOC-DPS, the light emitting layer with the light emitting wavelength of 560nm adopts a phosphorescence material m-PF-py, and the infrared light emitting layer with the light emitting wavelength of 780nm adopts Ir (mpbqx-g)2acac。
The distance from the infrared light-emitting layer to the reflective electrode is set to k lambda/4 n, wherein:
k is an integral multiple of 2, and k is 2 in the embodiment;
λ is the dominant wavelength of light emitted by the infrared light-emitting layer, in this example λ is 780 nm;
n is the refractive index of the organic functional layer, and in this example n is 1.8. Due to the influence of other factors in the actual manufacturing process, a certain difference exists between theoretical calculation and the actual device structure design, but the difference is within an allowable range.
The device provided by the embodiment is 12.6V when operated at a low temperature (-40 ℃) with fixed output brightness, and after 5 minutes of operation, the voltage is reduced to 10.5V under the same brightness, so that the operation characteristic of the device at the low temperature is effectively improved. Because the distance between the infrared layer and the reflecting electrode is selected, the infrared layer does not influence the light of other light-emitting layers, and because of the reason under infrared irradiation, more triplet excitons in the thermal activation delayed fluorescent material are converted into singlet excitons through reverse intersystem crossing to emit light, so that the luminous efficiency is improved, and the maximum external quantum efficiency of the device reaches 38%.
The specific device structure is as follows:
ITO/NPB(10nm)/TCTA(20nm)/mcp(30nm)：Ir(mpbqx-g)2acac4％/Bphen(30nm)/Bphen(10nm)：Mg 5％)/MoO3(10nm)/NPB(10nm)/DPEPO(20nm)：DMOC-DPS 10％/Bphen(10nm)/Bphen(10nm)：Mg 5％)/MoO3(10nm)/NPB(10nm)/TCTA(20nm)/mcp(30nm)：m-PF-py 12％/Bphen(30nm)/LiF(1nm)/Al(150nm)
the embodiment also provides a lighting device comprising the OLED device.
Example 3
Referring to fig. 2, the present embodiment provides an OLED device, which includes a first electrode 1, an organic functional layer 2, and a reflective electrode 3 sequentially disposed. The device structure of the embodiment is a single-layer structure, and the organic functional layer 2 includes two light emitting layers 21, namely an infrared light emitting layer and a blue thermal activation delayed fluorescence material light emitting layer, and the light emitting spectra are 700nm and 470nm respectively. The voltage of the device is 5.2V when the device is operated at a low temperature (-40 ℃) with fixed output brightness, and after 5 minutes of operation, the voltage is reduced to 4.3V under the same brightness, so that the operation characteristic of the device at the low temperature is effectively improved. And under the infrared irradiation, more triplet excitons in the thermal activation delayed fluorescent material are promoted to be converted into singlet excitons to emit light through reverse intersystem crossing, so that the luminous efficiency is improved, and the maximum external quantum efficiency of the device reaches 19.5%.
The specific device structure is as follows:
ITO/NPB(10nm)/DPEPO(20nm)：DMOC-DPS 10％/mcp(10nm)/Ga2(saph)2qz(30nm):NSeD 4％/Bphen(30nm)/LiF(1nm)/Al(150nm)
the embodiment also provides a display device comprising the OLED device.
Example 4
Referring to fig. 1, the present embodiment provides an OLED device, which includes a first electrode 1, an organic functional layer 2, and a reflective electrode 3 sequentially disposed. The device structure of the embodiment is a three-layer stacked device, the organic functional layer 2 has 3 independent light emitting layers 21, and a CGL charge generation layer 22 is disposed between the adjacent light emitting layers 21. The 3 different light-emitting layers in the organic functional layer respectively use a blue light-emitting layer with the wavelength of 470nm, an orange light-emitting layer with the wavelength of 560nm and an infrared light-emitting layer with the light-emitting spectrum of 2500nm, wherein the light-emitting layer with the light-emitting wavelength of 470nm adopts a thermal activation delayed fluorescence material DMOC-DPS, and the light-emitting layer with the light-emitting wavelength of 560nm adopts a fluorescence material 2,8-di (t-butyl) -5,11-di [4- (t-butyl) phenyl ] -6, 12-diphenylnaphthalene phenyl TBRu.
It is known to those skilled in the art that the light emitting wavelength of the light emitting layer depends on the light emitting material itself, and as technology develops, an infrared light emitting layer with different wavelength will appear; the infrared light emitting layer with the light emitting wavelength of 700-2500nm or even longer can achieve the same or similar purposes, and is within the protection scope of the application.
Comparative example 1
Referring to fig. 3, the present comparative example provides an OLED device including a first electrode 1, an organic functional layer 2, and a reflective electrode 3 sequentially disposed. The device structure of this comparative example is a double stack device, the organic functional layer 2 has two independent light emitting layers 21, and a CGL charge generation layer 22 is provided between the two light emitting layers 21. Two different light emitting layers in the organic functional layer respectively use blue light with the wavelength of 470nm and orange light with the wavelength of 560nm, wherein the light emitting layer with the light emitting wavelength of 470nm adopts a thermal activation delayed fluorescent material, and the light emitting layer with the light emitting wavelength of 560nm adopts a phosphorescent material. The maximum external quantum efficiency of the device is 31%.
The specific device structure is as follows:
ITO/NPB(10nm)/DPEPO(20nm)：DMOC-DPS 10％/Bphen(10nm)/Bphen(20nm)：Mg 5％)/MoO3(10nm)/NPB(10nm)/TCTA(20nm)/mcp(30nm)：m-PF-py 12％/Bphen(30nm)/LiF(1nm)/Al(150nm)
comparative example 2
Referring to fig. 4, the present comparative example provides an OLED device including a first electrode 1, an organic functional layer 2, and a reflective electrode 3 sequentially disposed. The device structure of the comparative example is a single-layer structure, the organic functional layer 2 comprises a light-emitting layer 21 which is a blue thermal activation delayed fluorescence material light-emitting layer, the light-emitting spectrum is 470nm, and the highest efficiency of the device is 14.5%.
The specific device structure is as follows:
ITO/NPB(10nm)/DPEPO(20nm)：DMOC-DPS 10％/Bphen(30nm)/LiF(1nm)/Al(150nm)
comparative example 3
Referring to fig. 4, the present comparative example provides an OLED device including a first electrode 1, an organic functional layer 2, and a reflective electrode 3 sequentially disposed. The device structure of the comparative example is a single-layer structure, the organic functional layer 2 includes a light-emitting layer 21 which is an infrared light-emitting layer, the light-emitting wavelength is 700nm, and the maximum efficiency of the device is 2.2%.
The specific device structure is as follows:
ITO/NPB(10nm)/Ga2(saph)2qz(30nm):NSeD 4％/Bphen(30nm)/LiF(1nm)/Al(150nm)
it can be seen from comparison of example 1 with comparative examples 1 and 3 that the maximum external quantum efficiency of example 1 is improved by 6% compared with comparative example 1 because the maximum luminous efficiency of the infrared light-emitting layer itself is only 2.2%; compared with the comparative example 2, the highest external quantum efficiency of the example 3 is improved by 5 percent; the infrared light emitting layer significantly improves the maximum external quantum efficiency of the device. Meanwhile, comparing example 3 with comparative examples 2 and 3, it can be seen that the outermost quantum efficiency of the OLED device having both the infrared light emitting layer and the thermal activation delayed fluorescent material light emitting layer in the organic functional layer is significantly higher than the outermost quantum efficiency of the OLED device having only the infrared light emitting layer and only the thermal activation delayed fluorescent material light emitting layer, and higher than the sum of the outermost quantum efficiencies of the OLED device having only the infrared light emitting layer and only the thermal activation delayed fluorescent material light emitting layer.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (7)
1. The OLED device is characterized by comprising a first electrode, an organic functional layer and a reflecting electrode which are sequentially arranged; the organic functional layer comprises at least one infrared light-emitting layer and at least one heat-activated delayed fluorescent material light-emitting layer.
2. The OLED device according to claim 1, wherein the distance from the light emitting center of the infrared light emitting layer to the reflective electrode is k λ/4n, where k is an integer multiple of 2, λ is the dominant wavelength of light emitted from the infrared light emitting layer, and n is the refractive index of the organic functional layer.
3. The OLED device of claim 1, wherein the infrared light-emitting layer emits light having a dominant wavelength in the range of 700nm to 2500 nm.
4. The OLED device according to claim 1, wherein the infrared light emitting layer material is an organic small molecule material, an organic polymer, a rare earth complex, a transition metal complex, a quantum dot, or an organic-inorganic hybrid perovskite material.
5. The OLED device of claim 1, wherein the OLED device structure is a single layer or a stacked layer structure.
6. The OLED device of claim 1, wherein the organic functional layer further comprises a visible light fluorescent light emitting layer and/or a visible light phosphorescent light emitting layer.
7. A lighting device or display device comprising an OLED device as claimed in any one of claims 1 to 6.
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