CN112467058A - Ternary exciplex composite material main body and OLED device preparation method thereof - Google Patents
Ternary exciplex composite material main body and OLED device preparation method thereof Download PDFInfo
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Abstract
The invention discloses a ternary exciplex composite material main body and preparation of an OLED device thereof, wherein the OLED device comprises: an anode, a cathode, an organic functional layer disposed between the anode and the cathode; the organic functional layer comprises a hole injection layer, an organic light-emitting layer, an electron transport layer and an electron injection layer which are sequentially arranged in the direction from the anode to the cathode; the organic luminous layer comprises a host composite material and a guest material, the host composite material is a ternary exciplex formed by mixing an electron donor, a first electron acceptor and a second electron acceptor, and the electron donor is The first electron acceptor isThe second electron acceptor is The guest material is selected from one or more of a thermal activity delayed fluorescence material, a triplet-triplet annihilation material, a fluorescence material and a phosphorescence material. The main body composite material has good electron transmission efficiency and thermal stability, is beneficial to enhancing the efficacy and the luminous efficiency of an OLED device, and is suitable for solution processing.
Description
Technical Field
The invention relates to the technical field of electroluminescent devices, in particular to a ternary exciplex composite material main body and preparation of an OLED device thereof.
Background
Organic light-emitting diodes (OLEDs for short) have the advantages of self-luminescence, fast response, wide visibility, low driving voltage, energy saving, lightness and thinness, flexible processing and the like, and greatly meet the requirement of consumers on continuous update of display technology. Meanwhile, the OLED device has wide application prospect and huge market demand in the field of illumination.
The Thermal Activated Delayed Fluorescence (TADF) material has an intramolecular electron donor (D) -electron acceptor (A) structure, the maximum theoretical efficiency can reach 100%, the singlet excited state and triplet excited state energy levels are close to 0.5-1.0 eV, and the TADF material is used as a main material of a light-emitting layer to form an OLED device and has the characteristics of high light-emitting efficiency, no need of Eu and Ir rare earth metal elements and low volume production cost; because the traditional single-component host material (1, 3-bis (carbazole-9-yl) benzene, abbreviated as mCP) has lower glass transition temperature (Tg) (-60 ℃) to deteriorate the performance of an OLED device, the new exciplex system host replaces the mCP host to be beneficial to solving the problems, and two materials with different existing transmission properties can be formed, so that the charge transmission capability is increased, the electron-hole transmission is more balanced, the driving voltage of light emission is reduced, and the performance and the stability of the device are improved. The existing exciplex main body system mainly focuses on the research of a binary D-A exciplex system, and the exciplex main body system with more than three elements is rarely reported, so that an OLED new structure system based on the ternary exciplex main body system has a space for further development.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a ternary exciplex composite material host and preparation of an OLED device thereof, aims to solve the limitations of the traditional single host and OLED devices based on a binary exciplex host system, and opens up a new technical route.
The technical scheme of the invention is as follows:
a ternary exciplex composite host OLED device, wherein the OLED device comprises: an anode, a cathode, and an organic functional layer disposed between the anode and the cathode; the organic functional layer comprises a hole injection layer, an organic light-emitting layer, an electron transport layer and an electron injection layer which are sequentially arranged in the direction from the anode to the cathode; the organic light-emitting layer comprises a host composite material and a guest material, wherein the host composite material is a ternary exciplex formed by mixing an electron donor, a first electron acceptor and a second electron acceptor, and the electron donor isThe first electron acceptor isThe second electron acceptor isThe guest material is selected from one or more of a delayed thermal activity delayed fluorescence material, a triplet-triplet annihilation material, a fluorescent material, and a phosphorescent material.
A preparation method of a ternary exciplex composite material main body OLED device comprises the following steps:
providing an anode;
sequentially forming a hole injection layer, an organic light-emitting layer, an electron transport layer and an electron injection layer on the anode by a solution method, wherein the hole injection layer, the organic light-emitting layer, the electron transport layer and the electron injection layer form an organic functional layer;
forming a cathode on the organic functional layer to obtain an OLED device;
alternatively, the first and second electrodes may be,
providing a cathode;
forming an electron injection layer, an electron transport layer, an organic light emitting layer and a hole injection layer on the cathode in sequence by a solution method, wherein the electron injection layer, the electron transport layer, the organic light emitting layer and the hole injection layer form an organic functional layer;
forming an anode on the organic functional layer to obtain an OLED device;
the material of the organic light-emitting layer comprises a host composite material and a guest material, wherein the host composite material is a ternary exciplex formed by mixing an electron donor, a first electron acceptor and a second electron acceptor, and the electron donor is The first electron acceptor isThe second electron acceptor is The guest material is selected from one or more of a thermal activity delayed fluorescence material, a triplet-triplet annihilation material, a fluorescence material and a phosphorescence material.
Has the advantages that: the ternary exciplex formed by mixing the electron donor with the chemical structure and the two electron acceptors has good electron transmission efficiency and thermal stability, can effectively capture excitons and balance carriers, and is an organic light-emitting layer formed by a host composite material and one or more of a thermal activity delayed fluorescent material, a triplet-triplet annihilation material, a fluorescent material and a phosphorescent material as a guest material, so that the efficacy efficiency and the luminous efficiency of an OLED device are enhanced; meanwhile, the electron donor and the two electron acceptors of the ternary exciplex are organic micromolecules, so that the ternary exciplex is suitable for processing and preparing OLED devices by a solution method; in addition, the ternary exciplex widens the composition of the OLED exciplex main body system. A new technical route is formed. The OLED device obtained as described above can be used as a display device, a white light illumination device, and the like.
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Fig. 1 is a schematic diagram illustrating the operation principle of energy transfer of an organic light emitting layer formed by a binary exciplex host (a) and a ternary exciplex host (b) respectively as a host and a guest (e.g., TADF material) according to an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of an upright OLED device according to an embodiment of the present invention.
FIG. 3 is a graph showing energy level comparison of materials of respective layers used for preparing OLED devices in examples 1 and 2 and comparative examples 1 and 2 in example 3 of the present invention.
Detailed Description
The invention provides a ternary exciplex composite material main body and preparation of an OLED device thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a ternary exciplex composite material main body OLED device, which comprises: the organic functional layer comprises a hole injection layer, an organic light emitting layer, an electron transport layer and an electron injection layer which are sequentially arranged from the anode to the cathode; the above-mentionedThe material of the organic light-emitting layer comprises a host composite material and a guest material, wherein the host composite material is a ternary exciplex formed by mixing an electron donor, a first electron acceptor and a second electron acceptor, and the electron donor is a ternary exciplex The first electron acceptor isThe second electron acceptor is The guest material is selected from one or more of a thermal activity delayed fluorescence material, a triplet-triplet annihilation material, a fluorescence material and a phosphorescence material.
In this embodiment, the adopted ternary exciplex formed by mixing the electron donor and the two electron acceptors with the above structure has good electron transfer efficiency and thermal stability, can effectively capture excitons and balance carriers, is an organic light emitting layer formed by a host composite material and one or more selected from a thermal activity delayed fluorescent material, a triplet-triplet annihilation material, a fluorescent material and a phosphorescent material as guest materials, and is beneficial to enhancing the efficacy efficiency and the light emitting efficiency of the OLED device; meanwhile, the electron donor and the two electron acceptors of the ternary exciplex are organic micromolecules, so that the ternary exciplex is suitable for processing and preparing OLED devices by a solution method; in addition, the ternary exciplex widens the composition of the OLED exciplex main body system. The OLED device obtained as described above can be used as a display device, a white light illumination device, and the like.
Referring to fig. 1, specifically, the operating principle (b) of energy transfer of an organic light emitting layer formed by a host composite material and a guest material (e.g., TADF material) is compared with the operating principle (a) of energy transfer of an organic light emitting layer formed by a host composite material and a guest material (e.g., TADF material) by a binary exciplex; it can be known that the organic light emitting layer formed by the host composite material and the guest material (e.g., TADF material) of the ternary exciplex has dual energy transfer channels, so that the organic light emitting layer has better electron transport efficiency, and can more effectively capture excitons and balance carriers, thereby enabling the OLED device based on the ternary exciplex of the present embodiment to have better light emitting performance and efficiency.
In one embodiment, the mass ratio of the electron donor, the first electron acceptor and the second electron acceptor is 1-10: 1: 1 to 10. Within the mass ratio range, the ternary exciplex formed by mixing the electron donor, the first electron acceptor and the second electron acceptor has better electron transmission efficiency and thermal stability, can effectively capture excitons and balance carriers, and is more favorable for enhancing the efficacy efficiency and the luminous efficiency of the OLED device as an organic light emitting layer formed by a host material composite and a guest material. Preferably, the guest material is a thermally active delayed fluorescence material.
In one embodiment, the thermally active delayed fluorescence material is selected from
In one embodiment, the triplet-triplet annihilation (TTA) material may be selected from, but is not limited to One or more of;
In one embodiment, the mass ratio of the host composite material to the guest material is 1 to 100: 1.
in one embodiment, the thickness of the organic light emitting layer may be 10 to 100nm, such as 10nm, 30nm, 50nm, 60nm, 100nm, etc.
In one embodiment, other hole function layers may be further disposed between the anode and the organic light emitting layer, such as at least one of a hole transport layer and an electron blocking layer; when the hole injection layer and the hole transport layer (or the electron blocking layer) are provided at the same time, the hole injection layer is provided near the anode, and the hole transport layer (or the electron blocking layer) is provided near the organic light emitting layer; when a hole injection layer, a hole transport layer and electricity are simultaneously providedAnd when the electron blocking layer is used as the electron blocking layer, the hole injection layer is arranged close to the anode, the electron blocking layer is arranged close to the organic light emitting layer, and the hole transmission layer is arranged between the hole injection layer and the electron blocking layer. The thickness of the hole injection layer is 50-80 nm, such as 50nm, 60nm, 80nm and the like; the material of the hole injection layer can be selected from, but is not limited to, 2, 3, 6, 7, 10, 11-hexacyano-1, 4, 5, 8, 9, 12-hexaazatriphenylene (HAT-CN), 4- (9- (2-ethylhexyl) -9H-carbazole-3, 6-diyl) diphenol (MO)3) Poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS), poly (4-styrenesulfonic acid) (structure isAbbreviated PSSA) modified (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (m-PEDOT: PSS), poly [ (9, 9-dioctylfluorenyl-2, 7-diyl) -co- (4,4' - (N- (p-butylphenyl)) diphenylamine)](TFB), poly (9-vinylcarbazole) (PVK), poly [ bis (4-phenyl) (4-butylphenyl) amine](Poly-TPD), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), 1-bis [4- [ N, N ' -bis (p-tolyl) amino group]Phenyl radical]Cyclohexane (TAPC), One or more of (a). The thickness of the hole transport layer is 50-80 nm, such as 50nm, 60nm, 80nm and the like; the material of the hole transport layer may be a hole transport layer material commonly used in the art. The thickness of the electron blocking layer is 5-20 nm, such as 5nm, 15nm, 20nm and the like; the material of the electron blocking layer may be an electron blocking material commonly used in the art.
In one embodiment, other electronic function layers such as a hole blocking layer may be disposed between the cathode and the organic light emitting layer, and an electron injection layer and an electron transport layer are disposed between the cathode and the organic light emitting layerAnd a hole blocking layer, the electron injection layer is disposed adjacent to the cathode, the hole blocking layer is disposed adjacent to the organic light emitting layer, and the electron transport layer is disposed between the electron injection layer and the hole blocking layer. The thickness of the electron injection layer is 1-10 nm, such as 1nm, 5nm, 10nm, etc.; the material of the electron injection layer can be, but is not limited to, 8-hydroxyquinoline-lithium (bLiq) or LiF. The thickness of the electron transport layer is 50-80 nm, for example, 50nm, 60nm, 80nm, and the like. The material of the electron transport layer can be, but is not limited to ZnO、TiO2、BaTiO3One or more of aluminum-doped zinc oxide, lithium-doped zinc oxide, magnesium-doped zinc oxide, CdS, ZnS, MoS, WS and CuS; the thickness of the hole blocking layer is 5-20 nm, such as 5nm, 15nm, 20nm and the like; the material of the hole blocking layer may be, but is not limited toOr bis-4, 6- (3, 5-di-4-pyridylphenyl) -2-methylpyrimidine or 4, 6-bis (3, 5-di (3-pyridine) ylphenyl) -2-methylpyrimidine or derivatives thereof.
In one embodiment, the material of the anode may be selected from, but not limited to, one or more of Indium Tin Oxide (ITO), aluminum doped zinc oxide (AZO), antimony doped tin oxide (ATO), and fluorine doped tin oxide (FTO).
In one embodiment, the material of the cathode may be selected from one or more of, but not limited to, Al, Ag, Cu, and Au.
Specifically, the ternary exciplex composite host OLED device of the present embodiment can be configured in different types, that is, the ternary exciplex composite host OLED device can be configured as an OLED device having a front-facing structure and can also be configured as an OLED device having an inverted structure. Now, taking an upright OLED device with a hole injection layer as a hole functional layer and an electron injection layer, an electron transport layer and a hole blocking layer as an electron functional layer as an example, the structure of the OLED device is further described, as shown in fig. 2, the OLED device sequentially includes from bottom to top: an anode 10, a hole functional layer 20 (i.e., a hole injection layer), an organic light emitting layer 30, an electron functional layer 40 (including a hole blocking layer 41, an electron transport layer 42, and an electron injection layer 43), a cathode 50; the material of the organic light-emitting layer 30 includes a host composite material and a guest material, the host composite material is a ternary exciplex formed by mixing an electron donor, a first electron acceptor and a second electron acceptor, wherein the electron donor is mCP, the first electron acceptor is DTDP-TRZ, and the second electron acceptor is OXD-7; the guest material is selected from one or more of a thermal activity delayed fluorescence material, a triplet-triplet annihilation material, a fluorescent material, and a phosphorescent material.
The embodiment of the invention also provides a preparation method of the ternary exciplex composite material main body OLED device, which comprises the following steps: including conventional upright device fabrication steps (S10, S20, S30) and inverted device fabrication steps (S10', S20', S30 ').
S10, providing an anode;
s20, sequentially forming a hole injection layer, an organic light-emitting layer, an electron transport layer and an electron injection layer on the anode by a solution method, wherein the hole injection layer, the organic light-emitting layer, the electron transport layer and the electron injection layer form an organic functional layer;
s30, forming a cathode on the organic functional layer to obtain the OLED device;
alternatively, the first and second electrodes may be,
s10', providing a cathode;
s20', forming an electron injection layer, an electron transport layer, an organic light-emitting layer and a hole injection layer on the cathode in sequence by a solution method, wherein the electron injection layer, the electron transport layer, the organic light-emitting layer and the hole injection layer form an organic functional layer;
s30', forming an anode on the organic functional layer to obtain the OLED device;
the material of the organic light-emitting layer comprises a host composite material and a guest material, wherein the host composite material is a ternary exciplex formed by mixing an electron donor, a first electron acceptor and a second electron acceptor, and the electron donor isThe first electron acceptor isThe second electron acceptor isThe guest material is selected from one or more of a thermal activity delayed fluorescence material, a triplet-triplet annihilation material, a fluorescence material and a phosphorescence material.
In one embodiment, in step S20, at least one of a hole transport layer and an electron blocking layer may be sequentially formed before forming the organic light emitting layer; the hole transport layer and the electron blocking layer may be sequentially formed by a solution method, for example, before the organic light emitting layer. In step S30, before forming the electron transport layer, a hole blocking layer may be further formed; the hole blocking layer may be thermally evaporated or solution deposited, for example, by physical vapor deposition prior to formation of the electron transport layer. In step S20', a hole blocking layer may be further formed before the organic light emitting layer is formed on the cathode; the hole blocking layer may be formed by a physical vapor deposition thermal evaporation method or a solution method, for example, before forming the organic light emitting layer on the cathode. In step S30', at least one of an electron blocking layer and a hole transporting layer may be further formed in this order before the hole injection layer is formed; the electron blocking layer and the hole transporting layer may be sequentially formed by a physical vapor deposition thermal evaporation method or a solution method, for example, before the hole injection layer is formed. That is, other functional layers may be prepared in the OLED device of this embodiment, and the material selection and thickness of each layer in the OLED device are the same as those described above, and are not described herein again.
In this embodiment, the preparation method of each layer may be a chemical method or a physical method, wherein the chemical method includes, but is not limited to, one or more of a chemical vapor deposition method, a continuous ion layer adsorption and reaction method, an anodic oxidation method, an electrolytic deposition method, and a coprecipitation method; the physical method includes, but is not limited to, one or more of solution method (such as spin coating, printing, knife coating, dip-coating, dipping, spraying, roll coating, casting, slit coating, or bar coating), evaporation method (such as thermal evaporation, electron beam evaporation, magnetron sputtering, or multi-arc ion plating), deposition method (such as physical vapor deposition, atomic layer deposition, pulsed laser deposition, etc.).
In one embodiment, the anode needs to be pretreated in order to obtain a high-quality hole-function layer when manufacturing the positive OLED device. Wherein the pretreatment process specifically comprises: the anode is cleaned and then treated with ultraviolet-ozone or oxygen plasma to further remove organic matter attached to the surface of the anode and increase the work function of the anode.
In one embodiment, the resulting OLED device is subjected to an encapsulation process. The packaging process can adopt common machine packaging or manual packaging. Preferably, the oxygen content and the water content in the packaging treatment environment are both lower than 1ppm so as to ensure the stability of the device.
The present invention will be described in detail below with reference to specific examples.
Example 1 preparation of ternary exciplex composite host OLED device
The structure of the red OLED device is ITO (anode)/m-PEDOT: PSS (hole injection layer, 60nm)/AQb1: mCP: DTDP-TRZ: OXD-7 (organic light emitting layer, 50nm, AQb1 is guest material, the mass ratio of ternary exciplex mCP: DTDP-TRZ: OXD-7 is 35:35:30)/DPEPO (hole blocking layer, 15nm)/TmPyPB (electron transport layer, 60nm)/Liq (electron injection layer, 1nm)/Al (cathode, 100 nm); the preparation method comprises the following steps:
(1) spin-coating a 60nm hole injection layer (m-PEDOT: PSS) on ITO glass at 4000r/min, and annealing at 120 deg.C for 10min in a glove box;
(2) spin-coating a 50nm organic light-emitting layer (AQb1: mCP: DTDP-TRZ: OXD-7 mass ratio of 10:35:35:30) on the hole injection layer at a rotation speed of 1000r/min in a nitrogen atmosphere, and annealing at 50 ℃ for 10 min;
(3) at a vacuum degree of 10-5A 15nm hole blocking layer (DPEPO) is deposited on the organic light-emitting layer under mbar;
(4) at a vacuum degree of 10-5Depositing a 60nm electron transport layer (material TmPyPB) on the hole blocking layer under mbar;
(5) at a vacuum degree of 10-5Depositing a 1nm electron injection layer (Liq material) on the electron transport layer under mbar;
(6) at a vacuum degree of 10-5And spinning and coating a layer of Al with the thickness of 100nm on the electron injection layer as a cathode under the mbar condition to obtain the red light OLED device.
Comparative example 1 preparation of an OLED device based on DTDP-TRZ
The structure of the red OLED device is ITO (anode)/m-PEDOT: PSS (hole injection layer, 60nm)/AQb1(10 wt%). DTDP-TRZ (organic light emitting layer, 50nm, AQb1 as guest material, DTDP-TRZ as host material)/DPEPO (hole blocking layer, 15nm)/TmPyPB (electron transport layer, 60nm)/Liq (electron injection layer, 1nm)/Al (cathode, 100 nm); the preparation method comprises the following steps:
(1) spin-coating a 60nm hole injection layer (made of m-PEDOT: PSS) on ITO glass at the rotating speed of 4000r/min, and annealing in a glove box at 120 ℃ for 15 min;
(2) spin-coating a 50nm organic light-emitting layer on the hole injection layer at a rotation speed of 1000r/min in a nitrogen atmosphere, (AQb1 wt% and DTDP-TRZ wt%) and annealing at 50 deg.C for 10 min;
(3) at a vacuum degree of 10-5A 15nm hole blocking layer (DPEPO) is deposited on the organic light-emitting layer under mbar;
(4) at a vacuum degree of 10-5Depositing a 60nm electron transport layer (material TmPyPB) on the hole blocking layer under mbar;
(5) at a vacuum degree of 10-5Depositing a 1nm electron injection layer (Liq material) on the electron transport layer under mbar;
(6) at a vacuum degree of 10-5And depositing a layer of Al with the thickness of 100nm on the electron injection layer as a cathode under the mbar condition to obtain the red light OLED device.
Example 2 preparation of OLED devices based on ternary exciplex
The structure of the red OLED device is ITO (anode)/m-PEDOT: PSS (hole injection layer, 60nm)/AQb1 mCP TDP-TRZ (TDP-TRZ structure is) OXD-7 (organic light-emitting layer, 50nm, AQb1 is guest material, mass ratio of ternary non-exciplex mCP: TDP-TRZ: OXD-7 is 35:35:30)/DPEPO (hole blocking layer, 15nm)/TmPyPB (electron transport layer, 60nm)/Liq (electron injection layer, 1nm)/Al (cathode, 100 nm); the preparation method of the red OLED device comprises the following steps:
(1) spin-coating a 60nm hole injection layer (made of m-PEDOT: PSS) on ITO glass at the rotating speed of 4000r/min, and annealing in a glove box at 120 ℃ for 10 min;
(2) spin-coating a 50nm organic light-emitting layer (AQb1: mCP: TDP-TRZ: OXD-7 mass ratio of 10:35:35:30) on the hole injection layer in a nitrogen atmosphere, and annealing at 50 deg.C for 10 min;
(3) at a vacuum degree of 10-5A 15nm hole blocking layer (DPEPO) is deposited on the organic light-emitting layer under mbar;
(4) at a vacuum degree of 10-5Depositing a 60nm electron transport layer (material TmPyPB) on the hole blocking layer under mbar;
(5) at a vacuum degree of 10-5Depositing a 1nm electron injection layer (Liq material) on the electron transport layer under mbar;
(6) at a vacuum degree of 10-5And depositing a layer of Al with the thickness of 100nm on the electron injection layer as a cathode under the mbar condition to obtain the red light OLED device.
Comparative example 2 preparation of TDP-TRZ-based OLED device
The structure of the red OLED device is ITO (anode)/m-PEDOT: PSS (hole injection layer, 60nm)/AQb1(10 wt%): TDP-TRZ (organic light emitting layer, 50nm, AQb1 as guest material, TDP-TRZ as host material)/DPEPO (hole blocking layer, 15nm)/TmPyPB (electron transport layer, 60nm)/Liq (electron injection layer, 1nm)/Al (cathode, 100 nm); the preparation method of the red OLED device comprises the following steps:
(1) spin-coating a 60nm hole injection layer (m-PEDOT: PSS) on the ITO glass, and annealing at 140 deg.C in air for 15 min;
(2) in a nitrogen atmosphere, an organic light-emitting layer (AQb1 content 10 wt%, 90 wt%) of 50nm was spin-coated on the hole injection layer, and annealing was performed at 50 ℃ for 10 min;
(3) at a vacuum degree of 10-5A 15nm hole blocking layer (DPEPO) is deposited on the organic light-emitting layer under mbar;
(4) at a vacuum degree of 10-5Depositing a 60nm electron transport layer (material TmPyPB) on the hole blocking layer under mbar;
(5) at a vacuum degree of 10-5Depositing a 1nm electron injection layer (Liq material) on the electron transport layer under mbar;
(6) at a vacuum degree of 10-5And depositing a layer of Al with the thickness of 100nm on the electron injection layer as a cathode under the mbar condition to obtain the red light OLED device.
Example 3 Performance test analysis of OLED devices
The energy levels of the materials of the respective layers used to fabricate the OLED devices according to examples 1 and 2 and comparative examples 1 and 2 are shown in fig. 3, and it can be seen that the TDP-TRZ and DTDP-TRZ having similar structures have slightly different energy levels.
The light emitting properties (luminance of 10 cd. m) of the OLED devices prepared in examples 1 and 2 and comparative examples 1 and 2-2Time on voltage (V)on) Characteristic emission peak (EL)peakA/nm) and a luminance of 10 to 1000 cd-m-2Maximum Current Efficiency (CE) in the rangemax/cd·A-1) Maximum Power Efficiency (PE)max/lm·W-1) And maximum External Quantum Efficiency (EQE)max(%)) and a luminance of 100cd · m-2The results of the test were shown in Table 1, based on the International Commission on illumination coordinates (CIE, (x, y))). It is known that, compared with DTDP-TRZ, the luminophores formed by ternary exciplexes (mCP, TDP-TRZ and OXD-7) as host composite materials and TADF materials as guest materials have better luminescence performance.
TABLE 1
The ratio of the performance parameter of the OLED device prepared in the example in table 1 to the performance parameter of the OLED device prepared in the corresponding comparative example was used as the gain of the performance parameter of the OLED device prepared in the example, and the gain was converted to obtain the partial performance parameters (CE) of the OLED device prepared in the examples 1 and 2max、PEmaxAnd EQEmax) The gain of the OLED device prepared in example 1 is 1.3 times the EQE gain of the OLED device prepared in example 2, as shown in table 2; shows that: compared with a ternary non-exciplex, the ternary exciplex has better application prospect as a main composite material.
TABLE 2
In summary, the invention provides a ternary exciplex composite material host and an OLED device preparation thereof, the ternary exciplex formed by mixing the electron donor and the two electron acceptors with the above structure adopted in the invention has good electron transfer efficiency and thermal stability, can effectively capture excitons and balance carriers, is a host composite material, and is an organic light emitting layer formed by taking one or more of a thermal activity delayed fluorescent material, a triplet-triplet annihilation material, a fluorescent material and a phosphorescent material as guest materials; the efficiency and the luminous efficiency of the OLED device are enhanced; meanwhile, the electron donor and the two electron acceptors of the ternary exciplex are organic micromolecules, so that the ternary exciplex is suitable for processing and preparing OLED devices by a solution method; in addition, the ternary exciplex widens the composition of the OLED exciplex main body system. The OLED device obtained as described above can be used as a display device, a white light illumination device, and the like.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A ternary exciplex composite host OLED device, comprising: an anode, a cathode, and an organic functional layer disposed between the anode and the cathode; the organic functional layer comprises a hole injection layer, an organic light-emitting layer, an electron transport layer and an electron injection layer which are sequentially arranged in the direction from the anode to the cathode; the organic light-emitting layer comprises a host composite material and a guest material, the host composite material is a ternary exciplex formed by mixing an electron donor, a first electron acceptor and a second electron acceptor, and the electron donor is The first electron acceptor isThe second electron acceptor is The guest material is selected from one or more of a thermal activity delayed fluorescence material, a triplet-triplet annihilation material, a fluorescence material and a phosphorescence material.
2. The OLED device as claimed in claim 1, wherein the mass ratio of the electron donor to the first electron acceptor to the second electron acceptor is 1-10: 1: 1 to 10.
6. The ternary exciplex composite host OLED device according to claim 1, wherein the mass ratio of the host composite material to the guest material is 1 to 100: 1.
7. the ternary exciplex composite host OLED device of claim 1, the hole injection layer is made of 2, 3, 6, 7, 10, 11-hexacyano-1, 4, 5, 8, 9, 12-hexaazatriphenylene, 4- (9- (2-ethylhexyl) -9H-carbazole-3, 6-diyl) diphenol, poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), poly (4-styrenesulfonic acid) -modified (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), and poly [ (9, 9-dioctylfluorenyl-2, 7-diyl) -co- (4,4' - (N- (p-butylphenyl)) diphenylamine).]Poly (9-vinylcarbazole), poly [ bis (4-phenyl) (4-butylphenyl) amine]N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine, 1-bis [4- [ N, N ' -di (p-tolyl) amino group]Phenyl radical]Cyclohexane, One or more of;
the material of the electron transport layer is ZnO、TiO2、BaTiO3One or more of aluminum-doped zinc oxide, lithium-doped zinc oxide, magnesium-doped zinc oxide, CdS, ZnS, MoS, WS and CuS;
the material of the electron injection layer is 8-hydroxyquinoline-lithium or LiF.
8. The ternary exciplex composite host OLED device of claim 1, wherein the anode material is selected from one or more of indium tin oxide, aluminum doped zinc oxide, antimony doped tin oxide, and fluorine doped tin oxide.
9. The ternary exciplex composite host OLED device of claim 1, wherein the cathode material is selected from one or more of Al, Ag, Cu and Au.
10. A preparation method of a ternary exciplex composite material main body OLED device is characterized by comprising the following steps:
providing an anode;
sequentially forming a hole injection layer, an organic light-emitting layer, an electron transport layer and an electron injection layer on the anode by a solution method, wherein the hole injection layer, the organic light-emitting layer, the electron transport layer and the electron injection layer form an organic functional layer;
forming a cathode on the organic functional layer to obtain the OLED device;
alternatively, the first and second electrodes may be,
providing a cathode;
forming an electron injection layer, an electron transport layer, an organic light emitting layer and a hole injection layer on the cathode in sequence by a solution method, wherein the electron injection layer, the electron transport layer, the organic light emitting layer and the hole injection layer form an organic functional layer;
forming an anode on the organic functional layer to obtain the OLED device;
the material of the organic light-emitting layer comprises a host composite material and a guest material, wherein the host composite material is a ternary exciplex formed by mixing an electron donor, a first electron acceptor and a second electron acceptor, and the electron donor isThe first electron acceptor isThe second electron acceptor isThe guest material is selected from one or more of a thermally activated delayed fluorescence material, a triplet-triplet annihilation material, a fluorescent material, and a phosphorescent material.
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