WO2022078094A1 - 发光器件、显示基板 - Google Patents

发光器件、显示基板 Download PDF

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WO2022078094A1
WO2022078094A1 PCT/CN2021/115907 CN2021115907W WO2022078094A1 WO 2022078094 A1 WO2022078094 A1 WO 2022078094A1 CN 2021115907 W CN2021115907 W CN 2021115907W WO 2022078094 A1 WO2022078094 A1 WO 2022078094A1
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light
group
substituted
unsubstituted
emitting device
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PCT/CN2021/115907
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English (en)
French (fr)
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孙海雁
张晓晋
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京东方科技集团股份有限公司
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Priority claimed from CN202011112314.2A external-priority patent/CN112234150B/zh
Application filed by 京东方科技集团股份有限公司 filed Critical 京东方科技集团股份有限公司
Priority to US17/789,683 priority Critical patent/US20230096510A1/en
Publication of WO2022078094A1 publication Critical patent/WO2022078094A1/zh

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    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • 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
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Definitions

  • the embodiments of the present invention belong to the technical field of organic light emitting diodes, and in particular relate to a light emitting device and a display substrate.
  • OLED Organic light-emitting diode
  • the light-emitting materials of organic light-emitting diodes mainly include phosphorescent materials and fluorescent materials. Based on the limitation of light-emitting principles, the light-emitting efficiency of conventional fluorescent materials is lower than that of phosphorescent materials, so their applications are greatly limited.
  • thermally activated delayed fluorescence (TADF) materials allow the conversion of non-radiative triplet excited states to radiative singlet states via inverse intersystem crossover (RISC), which can theoretically achieve 100% internal quantum efficiency (IQE); moreover, TADF materials usually do not contain heavy metals and do not cause pollution, so they have broad application prospects.
  • RISC inverse intersystem crossover
  • IQE internal quantum efficiency
  • the embodiments of the present invention at least partially solve the problems of difficult development, low efficiency and performance degradation of existing organic light emitting diode main materials using TADF materials, and provide a light emitting device and display substrate with high efficiency, narrow emission spectrum, and easily available materials.
  • an embodiment of the present invention provides a light-emitting device, which includes a cathode, an anode, and a first light-emitting layer and a second light-emitting layer disposed between the cathode and the anode, the first light-emitting layer is located close to the second light-emitting layer Anode side;
  • the first light-emitting layer includes a first host material and a first guest material, and the hole mobility of the first host material is higher than the electron mobility;
  • the second light-emitting layer includes a second host material and a second guest material, and the hole mobility of the second host material is higher than the electron mobility;
  • T1 represents the triplet excitation energy
  • S1 represents the singlet excitation energy
  • h1 represents the first host material
  • h2 represents the second host material
  • g1 represents the first guest material
  • g2 represents the second guest material
  • the second guest material is a thermally activated delayed fluorescent material
  • the full width at half maximum of the emission spectrum of the second guest material is less than or equal to 35 nm.
  • the energy of the light emitted by the first guest material accounts for less than 20%.
  • the mass percentage of the second host material is between 70% and 99%, and the mass percentage of the second guest material is between 1% and 30%. between.
  • the first body material and the second body material are the same material.
  • the thickness of the first light-emitting layer is between 5 nm and 15 nm.
  • the thickness of the second light-emitting layer is between 1 nm and 20 nm.
  • each L is independently selected from any one of a single bond, a substituted C6 to C30 arylene group, and an unsubstituted C6 to C30 arylene group;
  • the single bond refers to the R corresponding to L1 It is directly connected to the benzene ring through a single bond, or the AR1 corresponding to L is directly connected to N through a single bond;
  • AR1 is selected from substituted C6 to C30 aryl, unsubstituted C6 to C30 aryl, substituted C2 to C30 heterocyclyl, unsubstituted C2 to C30 heterocyclyl, substituted C6 to C30 aromatic Amine group, unsubstituted C6 to C30 arylamine group, substituted C8 to C30 aryl and heterocyclic group-containing groups, unsubstituted C8 to C30 aryl and heterocyclic group-containing groups any of the
  • Each R1 is independently selected from hydrogen, substituted C1 to C20 alkyl, unsubstituted C1 to C20 alkyl, substituted C6 to C30 aryl, unsubstituted C6 to C30 aryl, substituted C2 to C30 heterocyclyl, unsubstituted C2 to C30 heterocyclyl, substituted C8 to C30 aryl and heterocyclyl containing groups, unsubstituted C8 to C30 aryl and heterocyclyl containing groups Any one of the group, substituted nitrile group, unsubstituted nitrile group, substituted isonitrile group, unsubstituted isonitrile group, hydroxyl group and thiol group; there is no connection between R1 connected with different L, or connected to each other to form a ring structure;
  • At least one of AR1 and all R1 is selected from the group consisting of carbazolyl R(a), substituted carbazolyl R(a), bitriphenylene R(b), substituted bitriphenylene R(b) ) any of the following:
  • X1 is selected from C or N;
  • Each R2 is independently selected from any one of group A, substituted group A, group B, and substituted group B, and among all R2, at least two are group A or substituted group Group A, there is at least one group B or substituted group B;
  • the structural formula of the group A is any of the following:
  • X2 is selected from any one in N, O, S;
  • the structural formula of the group B is any of the following:
  • X3 is selected from O or S; each R3 is independently selected from hydrogen, halogen group, substituted silyl group, unsubstituted silyl group, nitrile group, substituted C1 to C20 alkyl, unsubstituted C1 to C20 alkyl, substituted C1 to C20 alkoxy, unsubstituted C1 to C20 alkoxy, substituted C6 to C30 aryl, unsubstituted C6 to C30 aryl, substituted Any of a C2 to C30 heterocyclic group and an unsubstituted C2 to C30 heterocyclic group.
  • the second guest material has the following general formula 3:
  • each R4 is independently selected from hydrogen, halogen group, substituted silyl group, unsubstituted silyl group, nitrile group, substituted C1 to C20 alkyl group, unsubstituted C1 to C20 alkyl group , substituted C1 to C20 alkoxy, unsubstituted C1 to C20 alkoxy, substituted C6 to C30 aryl, unsubstituted C6 to C30 aryl, substituted C2 to C30 heterocyclyl , any one of unsubstituted C2 to C30 heterocyclic groups;
  • Each X4 is independently selected from any one of single bond, O, S, N-R5; the single bond refers to that the two benzene rings connected to X4 are directly connected by a single bond; R5 is selected from hydrogen, halogen group, substituted silyl, unsubstituted silyl, nitrile, substituted C1 to C20 alkyl, unsubstituted C1 to C20 alkyl, substituted C1 to C20 alkoxy, unsubstituted of C1 to C20 alkoxy, substituted C6 to C30 aryl, unsubstituted C6 to C30 aryl, substituted C2 to C30 heterocyclyl, unsubstituted C2 to C30 heterocyclyl any kind.
  • an embodiment of the present invention provides a display substrate, which includes a base and at least one light-emitting device disposed on the base;
  • At least one light-emitting device is the above-mentioned light-emitting device.
  • the display substrate is a display substrate.
  • FIG. 1 is a schematic structural diagram of a light-emitting device according to an embodiment of the present invention
  • FIG. 2 is a schematic diagram of energy interaction of a light-emitting device according to an embodiment of the present invention
  • FIG. 3 is a schematic structural diagram of another light-emitting device according to an embodiment of the present invention.
  • 5 is an emission spectrum of a light-emitting device and an emission spectrum of a first guest material according to an embodiment of the present invention
  • FIG. 6 is the emission spectra of Comparative Example 1, Comparative Example 2, and Example 1 of the embodiments of the present invention.
  • an embodiment of the present invention provides a light-emitting device, which includes a cathode, an anode, and a first light-emitting layer and a second light-emitting layer disposed between the cathode and the anode, the first light-emitting layer is located close to the second light-emitting layer Anode side;
  • the first light-emitting layer includes a first host material and a first guest material, and the hole mobility of the first host material is higher than the electron mobility;
  • the second light-emitting layer includes a second host material and a second guest material, and the hole mobility of the second host material is higher than the electron mobility;
  • T1 represents the triplet excitation energy
  • S1 represents the singlet excitation energy
  • h1 represents the first host material
  • h2 represents the second host material
  • g1 represents the first guest material
  • g2 represents the second guest material
  • the second guest material is a thermally activated delayed fluorescent material
  • the light-emitting device includes an anode (Aonde), a cathode (Cathode), and a first light-emitting layer (EML1) and a second light-emitting layer (EML2) sandwiched between the cathode and the anode, wherein the first light-emitting layer (EML1) and the second light-emitting layer (EML2) A light-emitting layer is closer to the anode than the second light-emitting layer.
  • the two light-emitting layers respectively include respective host materials (first host material, second host material) and guest materials (first guest material, second guest material), so that the light-emitting device is an organic light-emitting diode (OLED) emitting light device.
  • host materials first host material, second host material
  • guest materials first guest material, second guest material
  • each material of each light-emitting layer also satisfies the following properties:
  • the hole mobility of the host material is higher than the electron mobility.
  • the singlet excitation energy (S1) and triplet excitation energy (T1) of the host material are higher than the corresponding energy of the guest material; at the same time, the difference between S1 and T1 of the guest material is less than 0.1 eV (electron volt), that is, the energy band difference (band gap) ⁇ E ST of the guest material is small.
  • At least the second guest material is a thermally activated delayed fluorescence (TADF) material, that is, a material capable of emitting thermally activated delayed fluorescence.
  • TADF thermally activated delayed fluorescence
  • At least 40% of the emission spectrum of the first light-emitting layer coincides with the absorption spectrum of the second light-emitting layer.
  • the emission spectrum of the first light-emitting layer (the abscissa is the wavelength, the ordinate is the light intensity) covers a certain area, and the absorption spectrum of the second light-emitting layer also covers a certain area, then the first light-emitting layer
  • the area covered by the emission spectrum of the second light-emitting layer overlaps with the area covered by the absorption spectrum of the second light-emitting layer by at least 40% in area.
  • S0 represents the ground state energy
  • 25% and 75% at "electron excitation” indicate that according to basic physical principles, after the electron-hole recombination, there are 25% of the singlet state energy and 75% of the triplet state energy.
  • the first host material and the second host material are taken as an example of the same material, that is, T1(h1) and T1(h2) of the two host materials are equal, and S1(h1) and S1(h2) are also equal.
  • T1(h1)/T1(h2) of the host material of the first light-emitting layer/second light-emitting layer T1(g1) of the guest material of the first light-emitting layer and T1(g2) of the guest material of the second light-emitting layer between them, good Dexter energy transfer can occur respectively; thus, the energy can be transferred to the triplet state of the two guest materials, and then the reverse intersystem crossing (RISC) of the TADF material can be used to transfer the energy to the singlet state.
  • RISC reverse intersystem crossing
  • the S1(h1)/S1(h2) of the host material of the first light-emitting layer/the second light-emitting layer is the same as that of the first light-emitting layer.
  • the electron holes in the first light-emitting layer and the second light-emitting layer can recombine to form excitons, but the second light-emitting layer mainly (or all) emits light, so that certain To a certain extent, the separation of the luminescent center and the recombination center can be realized, the non-radiative effect can be reduced, and the device stability can be improved; at the same time, the above structure can realize the energy transfer of various channels, so as to realize the efficient utilization of triplet excitons, reduce self-quenching, and improve the stability of the device. Moreover, the above two light-emitting layers only need to meet simple energy level and spectral requirements, so the range of optional materials is wide, and there is no problem of difficulty in material development.
  • the full width at half maximum (FWHM) of the emission spectrum of the second guest material is less than or equal to 35 nm.
  • the light-emitting device of the embodiment of the present invention mainly relies on the second guest material to emit light, so the emission spectrum of the second guest material should be narrow, so that the color of the light emitted is "pure" and the color gamut is further improved.
  • the proportion of the energy of the light emitted by the first guest material is less than 20%.
  • the mass percentage content of the first host material is between 60% and 95%, and the mass percentage content of the first guest material is between 5% and 40%;
  • the mass percentage content of the second host material is between 70% and 99%, and the mass percentage content of the second guest material is between 1% and 30%.
  • the mass percentage content of the first host material may be between 60% and 95%, further between 70% and 90%, and further between 75% and 85%;
  • the mass percentage content of the guest material may be between 5% and 40%, further between 10% and 30%, and further between 15% and 25%.
  • the mass percentage content of the second host material is between 70% and 99%, further between 80% and 95%, and further between 85% and 90%;
  • the mass percentage content of the guest material is between 1% and 30%, further between 5% and 20%, and further between 10% and 15%.
  • the mass percentage of B means that B is a part of A, and when the mass of the whole A (including B) is taken as 100%, the relative percentage of the mass of B.
  • At least one of the first host material, the first guest material, and the second host material is a thermally activated delayed fluorescent material.
  • one or more of the first host material, the first guest material, and the second host material may also be TADF materials, so as to further improve the luminous efficiency.
  • the first body material and the second body material are the same material.
  • the first body material and the second body material may be the same material.
  • the thickness of the first light-emitting layer is between 5 nm and 15 nm.
  • the thickness of the second light-emitting layer is between 1 nm and 20 nm.
  • the thickness of the first light-emitting layer may be between 5 nm and 15 nm, and further may be between 8 nm and 12 nm.
  • the thickness of the second light-emitting layer may be between 1 nm and 20 nm, and further may be between 5 nm and 15 nm.
  • the light-emitting device further includes at least one of the following structures:
  • the anode of the light-emitting device is provided on the substrate, and starting from the anode, the light-emitting device may sequentially include: an anode (Aonde), a hole injection layer (HIL), a hole transport layer in a direction gradually away from the substrate. (HTL), electron blocking layer (EBL), first emission layer (EML1), second emission layer (EML2), hole blocking layer (HBL), electron transport layer (ETL), electron injection layer (EIL), cathode (Cathode), cover layer (CPL, Capping Layer), encapsulation layer (EN).
  • an anode Aonde
  • HIL hole injection layer
  • HTL hole transport layer in a direction gradually away from the substrate.
  • EBL electron blocking layer
  • EML1 first emission layer
  • EML2 hole blocking layer
  • HBL electron transport layer
  • EIL electron injection layer
  • CPL Capping Layer
  • encapsulation layer EN
  • the anode (Aonde) is the "positive electrode" of the light-emitting device, which can be a material with a high work function; when the light is emitted from the anode side (for example, the light-emitting device adopts a bottom emission structure), the anode can be a transparent oxide ITO (indium oxide) tin), IZO (zinc tin oxide), etc., the thickness can be 80-200nm; when the light is emitted from the cathode side (for example, the light-emitting device adopts a top emission structure), the anode can adopt a composite structure of metal and transparent oxide layer, such as "Ag (silver)/ITO" or "Ag/IZO", etc., where the thickness of the metal layer can be 80nm-100nm, and the thickness of the metal oxide measuring part can be 5nm-10nm, so that the reference value of the overall reflectivity of the anode can reach 85% ⁇ 95%.
  • ITO indium oxide
  • the hole injection layer (HIL), whose main function is to reduce the barrier of hole injection and improve the hole injection efficiency, can be HAT-CN(2,3,6,7,10,11-hexacyano-1 ,4,5,8,9,12-hexaazatriphenylene), CuPc (copper phthalocyanine) and other materials can also be obtained by P-type doping of the hole transport layer material, such as is NPB(N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine): F4TCNQ(2,3,5,6 -Tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone), TAPC(4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline] ): MnO 3 (manganese trioxide), etc., wherein the doping concentration (
  • the hole transport layer is mainly used for hole transport.
  • Materials with high hole mobility such as carbazole materials, can be used.
  • the highest occupied orbital (HOMO) energy level of the material is -5.2eV ⁇ Between -5.6eV, the thickness can be between 100nm and 140nm.
  • the electron blocking layer (EBL) whose main function is to transport holes and block electrons and excitons generated by the light-emitting layer, can be 1nm-10nm thick.
  • the first light-emitting layer (EML1) that is, the above-mentioned first light-emitting layer, can be formed by co-evaporation of the first host material and the first guest material.
  • the second light-emitting layer (EML2) that is, the above-mentioned second light-emitting layer, can be formed by co-evaporation of the second host material and the second guest material.
  • the hole blocking layer (HBL) whose main function is to transport electrons and block the excitons generated by the holes and the light-emitting layer, has a thickness of 2nm to 10nm.
  • Electron transport layer which is mainly used to transport electrons, can be formed by blending thiophenes, imidazoles, azine derivatives, etc. with lithium quinolate, wherein the mass percentage of lithium quinolate can be 30% to 70%. %;
  • the thickness of the electron transport layer can be between 20nm and 70nm.
  • Electron injection layer which is mainly used to improve the efficiency of electron injection, can use LiF (lithium fluoride), LiQ (tert-butyl lithium), Yb (ytterbium), Ca (calcium) and other materials; the thickness of the electron injection layer Can be in 0.5nm ⁇ 2nm.
  • Cathode which is the "negative electrode” of the light-emitting device, can be made of metal materials such as Mg (magnesium), Ag (silver), Al (aluminum), or an alloy material of Mg:Ag (where the mass ratio of Mg:Ag is It can be 3:7 ⁇ 1:9); when the light is emitted from the cathode side (such as the light-emitting device adopts a top emission structure), the thickness of the cathode can be 10nm-20nm, and when the light is emitted from the anode side (such as the light-emitting device adopts a bottom emission structure) ), the cathode thickness can be above 80nm to ensure good reflectivity.
  • metal materials such as Mg (magnesium), Ag (silver), Al (aluminum), or an alloy material of Mg:Ag (where the mass ratio of Mg:Ag is It can be 3:7 ⁇ 1:9); when the light is emitted from the cathode
  • the cover layer (CPL) has a high refractive index to adjust the light and form a resonant microcavity to improve the color of the light; the refractive index of the cover layer for light with a wavelength of 460nm should be greater than 1.8, which can be formed by vapor-deposited organic small molecule materials , the thickness can be 50nm ⁇ 80nm.
  • Encapsulation layer which is used to "enclose” the other structures of the light-emitting device, so that they (especially the light-emitting layer) are protected from external water, oxygen, etc.; the encapsulation layer can use sealant or encapsulation A thin film, or a composite structure in which an organic layer and an inorganic layer are stacked can be used.
  • first host material and the second host material are independently selected from materials having the following general formula 1:
  • AR1 is selected from substituted C6 to C30 aryl, unsubstituted C6 to C30 aryl, substituted C2 to C30 heterocyclyl, unsubstituted C2 to C30 heterocyclyl, substituted C6 to C30 aromatic Amine group, unsubstituted C6 to C30 arylamine group, substituted C8 to C30 aryl and heterocyclic group-containing groups, unsubstituted C8 to C30 aryl and heterocyclic group-containing groups any of the
  • Each R1 is independently selected from hydrogen, substituted C1 to C20 alkyl, unsubstituted C1 to C20 alkyl, substituted C6 to C30 aryl, unsubstituted C6 to C30 aryl, substituted C2 to C30 heterocyclyl, unsubstituted C2 to C30 heterocyclyl, substituted C8 to C30 aryl and heterocyclyl containing groups, unsubstituted C8 to C30 aryl and heterocyclyl containing groups Any one of the group, substituted nitrile group, unsubstituted nitrile group, substituted isonitrile group, unsubstituted isonitrile group, hydroxyl group and thiol group; there is no connection between R1 connected with different L, or connected to each other to form a ring structure;
  • connection mode of the L-R1 chain on the benzene ring in the above general formula 1 indicates that each L-R1 chain can be connected to any connectable position of the corresponding benzene ring, so that two L-R1 chains on each benzene ring can be connected.
  • the -R1 chain can be in any positional relationship such as ortho, para, and meta.
  • connection between R1 connected to different L, or connected to each other to form a ring structure means that in each molecule of general formula 1, there may be no direct connection between two different L-R1 chains, or , a connection can also be formed between the R1s of the two L-R1 chains (provided that a connection can be formed between the two R1s), thereby forming a cyclic structure.
  • the two L-R1 chains connected to each other to form a ring are usually "adjacent", such as connected to the same benzene ring, and further located in the ortho position.
  • group A is a single bond
  • absence of group A, that is, the two groups respectively connected to group A are actually directly connected directly through a single bond; the same below.
  • substituted group A refers to a group formed after at least one hydrogen of group A is substituted by other elements or groups, for example, hydrogen can be replaced by halogen, short chain (such as C1-C5) After the alkyl, aryl, etc. are substituted; the same below.
  • unsubstituted group A means that the hydrogen of group A cannot be substituted by other groups; the same below.
  • the group A when the group A is hydrogen element, it also includes the isotope of hydrogen, especially the isotope deuterium (D), because deuterium is relatively heavy, which is beneficial to improve the stability of the molecule; the same below.
  • D isotope deuterium
  • group A containing an aryl group and a heterocyclic group means that in the group A, both an aromatic ring and a heterocyclic ring are contained, or the group A is a "mixture" of an aryl group and a heterocyclic group; The same below.
  • the first guest material has the following general formula 2:
  • X1 is selected from C (carbon) or N (nitrogen);
  • X2 is selected from any one in N (nitrogen), O (oxygen), S (sulfur);
  • X3 is selected from O (oxygen) or S (sulfur); each R3 is independently selected from hydrogen, halogen group, substituted silyl group, unsubstituted silyl group, nitrile group, substituted C1 to C20 alkyl, unsubstituted C1 to C20 alkyl, substituted C1 to C20 alkoxy, unsubstituted C1 to C20 alkoxy, substituted C6 to C30 aryl, unsubstituted C6 to C30 Any one of the aryl group, the substituted C2 to C30 heterocyclic group, and the unsubstituted C2 to C30 heterocyclic group.
  • R3 when the above R3 is substituted alkyl or substituted alkoxy, its hydrogen is preferably substituted by halogen, that is, it can be haloalkyl or haloalkoxy; further, if there is hydrogen in haloalkyl or haloalkoxy, These hydrogens can then be substituted by other non-halogen groups, ie substituted haloalkyl or substituted haloalkoxy.
  • the second guest material has the following general formula 3:
  • Each X4 is independently selected from any one of single bond, O (oxygen), S (sulfur), N (nitrogen)-R5; single bond means that the two benzene rings connected to X4 are directly connected by a single bond
  • R5 is selected from hydrogen, halogen group, substituted silyl group, unsubstituted silyl group, nitrile group, substituted C1 to C20 alkyl, unsubstituted C1 to C20 alkyl, substituted C1 to C20 alkoxy, unsubstituted C1 to C20 alkoxy, substituted C6 to C30 aryl, unsubstituted C6 to C30 aryl, substituted C2 to C30 heterocyclyl, unsubstituted C2 to C30 Any of the heterocyclic groups of C30.
  • R4 when the above R4 is substituted alkyl or substituted alkoxy, its hydrogen is preferably substituted by halogen, that is, it can be haloalkyl or haloalkoxy; further, if there is hydrogen in haloalkyl or haloalkoxy, These hydrogens can then be substituted by other non-halogen groups, ie substituted haloalkyl or substituted haloalkoxy.
  • Embodiment 1 (refer to the bottom emission structure of FIG. 3 ):
  • EML represents a single light-emitting layer in the comparative example.
  • the first bracket after each structure indicates the material used in the structure, and if it is a mixture of multiple materials, the percentage indicates the mass percentage of the corresponding material; the second bracket after the structure indicates the thickness of the structure.
  • first host material and the second host material used in Example 1 are the same, and are the same as the host materials of the light-emitting layers in Comparative Example 1 and Comparative Example 2.
  • the energy levels of the first host material/second host material (both are the same), the first guest material, and the second guest material used in Example 1 are as follows:
  • the emission spectrum of the first light-emitting layer and the absorption spectrum of the second light-emitting layer in Example 1 are referred to FIG.
  • the emission spectrum of the first guest material and the emission spectrum of the light-emitting device in Example 1 refer to FIG. 5 . It can be seen that at the main peak corresponding to the emission spectrum of the first guest material, the emission spectrum of the light-emitting device is completely flat (that is, the light-emitting device does not emit light at this wavelength). This shows that the light emitted by the light-emitting device has no components from the first guest material at all, that is, in the light emitted by the light-emitting device, the proportion of the energy of the light emitted by the first guest material is 0% (of course, in line with "less than 20" %" requirement).
  • the light-emitting device of the embodiment of the present invention has higher luminous efficiency, can utilize energy more fully, and has narrow luminous spectrum and better color gamut.
  • At least one light-emitting device is the above-mentioned light-emitting device.
  • a plurality of light-emitting devices can be arranged on one substrate, and by controlling these light-emitting devices to emit light with desired brightness, a display substrate capable of displaying images can be obtained.
  • the display substrate of the embodiment of the present invention is also an organic light-emitting diode (OLED) display substrate.
  • the display substrate may further include gate lines, data lines, pixel circuits (eg, 2T1C pixel circuits, 7T1C pixel circuits) and other structures for controlling the light-emitting device to emit light.
  • gate lines data lines
  • pixel circuits eg, 2T1C pixel circuits, 7T1C pixel circuits
  • other structures for controlling the light-emitting device to emit light.
  • the light-emitting devices in the display substrate can be divided into different colors, so as to realize color display.
  • an embodiment of the present invention provides a display device including the above-mentioned display substrate.
  • the above-mentioned display substrate is assembled with other devices (eg, cell-aligning substrate, driving device, power supply, casing, etc.) to obtain a display device that can be used independently.
  • other devices eg, cell-aligning substrate, driving device, power supply, casing, etc.
  • the display device can be any product or component with display function, such as organic light emitting diode (OLED) display panel, electronic paper, mobile phone, tablet computer, TV, monitor, notebook computer, digital photo frame, navigator, etc.
  • OLED organic light emitting diode

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Abstract

本发明实施例提供一种发光器件、显示基板，属于有机发光二极管技术领域。本发明实施例的发光器件的第一发光层包括第一主体材料和第一客体材料；第二发光层包括第二主体材料和第二客体材料；S1(h1)>S1(g1)，T1(h1)>T1(g1)，S1(g1)-T1(g1)≤0.1eV；S1(h2)>S1(g2)，T1(h2)>T1(g2)，S1(g2)-T1(g2)≤0.1eV；S1(h1)≥S1(h2)>S1(g1)>S1(g2)，T1(h1)≥T1(h2)>T1(g1)>T1(g2)；第二客体材料为TADF材料；第一发光层的发射光谱所覆盖区域中，有至少40％的面积与第二发光层的吸收光谱所覆盖区重叠。

Description

发光器件、显示基板 技术领域
本发明实施例属于有机发光二极管技术领域，具体涉及一种发光器件、显示基板。
背景技术
有机发光二极管(OLED)发光器件因具有主动发光、响应速度快、能量利用率高、寿命长、易实现柔性等优点，在显示等领域获得了广泛应用。
有机发光二极管的发光材料主要包括磷光材料和荧光材料，基于发光原理限制，常规荧光材料的发光效率比磷光材料的发光效率低，故其应用受到了很大限制。而热活化延迟荧光(TADF)材料允许通过反向系统间交叉(RISC)将非辐射三线态激发态转换为辐射单线态，从而其理论上可实现100％的内部量子效率(IQE)；而且，TADF材料通常不含重金属，不会引起污染，故具有广泛的应用前景。
但是，TADF材料在有机发光二极管中的实际应用仍存在一些问题，如双注入特性良好的主体材料开发困难、主体材料与激子阻挡层的匹配不佳、易产生载流子不平衡导致发光效率降低、易产生界面激子堆积造成性能劣化等。
发明内容
本发明实施例至少部分解决现有采用TADF材料的有机发光二极管主体材料开发困难、效率不高、性能劣化的问题，提供一种效率高、发光光谱窄、材料易得的发光器件、显示基板。
第一方面，本发明实施例提供一种发光器件，其包括阴极、阳极，以及设于阴极和阳极间的第一发光层、第二发光层，所述第一发光层位于第二发光层靠近阳极一侧；其中，
所述第一发光层包括第一主体材料和第一客体材料，所述第一主体材料的空穴迁移率高于电子迁移率；
所述第二发光层包括第二主体材料和第二客体材料，所述第二主体材料的空穴迁移率高于电子迁移率；
S1(h1)>S1(g1)，T1(h1)>T1(g1)，S1(g1)-T1(g1)≤0.1eV；
S1(h2)>S1(g2)，T1(h2)>T1(g2)，S1(g2)-T1(g2)≤0.1eV；
S1(h1)≥S1(h2)>S1(g1)>S1(g2)，T1(h1)≥T1(h2)>T1(g1)>T1(g2)；
其中T1表示三线态激发能量，S1表示单线态激发能量，h1表示第一主体材料，h2表示第二主体材料，g1表示第一客体材料，g2表示第二客体材料；
所述第二客体材料为热活化延迟荧光材料；
所述第一发光层的发射光谱所覆盖区域中，有至少40％的面积与第二发光层的吸收光谱所覆盖区重叠。
可选的，所述第二客体材料的发射光谱的半峰全宽小于或等于35nm。
可选的，所述发光器件发出的光中，由所述第一客体材料发出的光的能量的占比小于20％。
可选的，所述第一发光层中，所述第一主体材料的质量百分含量在60％至95％之间，所述第一客体材料的质量百分含量在5％至40％之间；
可选的，所述第二发光层中，所述第二主体材料的质量百分含量在70％至99％之间，所述第二客体材料的质量百分含量在1％至30％之间。
可选的，所述第一主体材料、第一客体材料、第二主体材料中的至少一者为热活化延迟荧光材料。
可选的，所述第一主体材料和第二主体材料为相同的材料。
可选的，所述第一发光层的厚度在5nm至15nm之间。
可选的，所述第二发光层的厚度在1nm至20nm之间。
可选的，所述发光器件还包括以下结构的至少一种：
空穴注入层、空穴传输层、空穴阻挡层、电子注入层、电子传输层、电子阻挡层、覆盖层、封装层。
可选的，所述第一主体材料和第二主体材料分别独立的选自具有以下通式1的材料：
Figure PCTCN2021115907-appb-000001
其中，每个L分别独立的选自单键、取代的C6至C30的亚芳基、未取代的C6至C30的亚芳基中的任意一种；所述单键是指与L对应的R1直接通过单键与苯环连接，或与L对应的AR1直接通过单键与N连接；
AR1选自取代的C6至C30的芳基、未取代的C6至C30的芳基、取代的C2至C30的杂环基、未取代的C2至C30的杂环基、取代的C6至C30的芳香胺基、未取代的C6至C30的芳基胺基、取代的C8至C30的含有芳基和杂环基的基团、未取代的C8至C30的含有芳基和杂环基的基团中的任意一种；
每个R1分别独立的选自氢、取代的C1至C20的烷基、未取代的C1至C20的烷基、取代的C6至C30的芳基、未取代的C6至C30的芳基、取代的C2至C30的杂环基、未取代的C2至C30的杂环基、取代的C8至C30的含有芳基和杂环基的基团、未取代的C8至C30的含有芳基和杂环基的基团、取代的腈基、未取代的腈基、取代的异腈基、未取代的异腈基、羟基、硫醇基中的任意一种；与不同L连接的R1之间无连接，或相互连接形成环结构；
AR1和所有的R1中，有至少一个选自咔唑基R(a)、取代的咔唑基R(a)、联亚三苯基R(b)、取代的联亚三苯基R(b)中的任意一种：
所述R(a)的结构式为：
Figure PCTCN2021115907-appb-000002
所述R(b)的结构式为：
Figure PCTCN2021115907-appb-000003
可选的，所述第一客体材料具有以下通式2：
Figure PCTCN2021115907-appb-000004
其中，X1选自C或N；
每个R2分别独立的选自基团A、取代的基团A、基团B、取代的基团B中的任意一种，且所有R2中，有至少两个为基团A或取代的基团A，有至少一个为基团B或取代的基团B；
所述基团A的结构式为以下任意一种：
Figure PCTCN2021115907-appb-000005
其中，X2选自N、O、S中的任意一种；
所述基团B的结构式为以下任意一种：
Figure PCTCN2021115907-appb-000006
Figure PCTCN2021115907-appb-000007
其中，X3选自O或S；每个R3分别独立的选自氢、卤素基团、取代的甲硅烷基、未取代的甲硅烷基、腈基、取代的C1至C20的烷基、未取代的C1至C20的烷基、取代的C1至C20的烷氧基、未取代的C1至C20的烷氧基、取代的C6至C30的芳基、未取代的C6至C30的芳基、取代的C2至C30的杂环基、未取代的C2至C30的杂环基中的任意一种。
可选的，所述第二客体材料具有以下通式3：
Figure PCTCN2021115907-appb-000008
其中，每个R4分别独立的选自氢、卤素基团、取代的甲硅烷基、未取代的甲硅烷基、腈基、取代的C1至C20的烷基、未取代的C1至C20的烷基、取代的C1至C20的烷氧基、未取代的C1至C20的烷氧基、取代的C6至C30的芳基、未取代的C6至C30的芳基、取代的C2至C30的杂环基、未取代的C2至C30的杂环基中的任意一种；
每个X4分别独立的选自单键、O、S、N-R5中的任意一种；所述单键是指与X4连接的两个苯环直接通过单键连接；R5选自氢、卤素基团、取代的甲硅烷基、未取代的甲硅烷基、腈基、取代的C1至C20的烷基、未取代的C1至C20的烷基、取代的C1至C20的烷氧基、未取代的C1至C20的烷氧基、取代的C6至C30的芳基、未取代的C6至C30的芳基、取代的C2至C30的杂环基、未取代的C2至C30的杂环基中的任意一种。
第二方面，本发明实施例提供一种显示基板，其包括基底和设于所述基底上的至少一个发光器件；
所有所述发光器件中，有至少一个发光器件为上述的发光器件。
可选的，所述显示基板为显示基板。
附图说明
图1为本发明实施例的一种发光器件的结构示意图；
图2为本发明实施例的一种发光器件的能量交互原理图；
图3为本发明实施例的另一种发光器件的结构示意图；
图4为本发明实施例的一种发光器件的中第一发光层的发射光谱与第二发光层的吸收光谱；
图5为本发明实施例的一种发光器件的发射光谱与第一客体材料的发射光谱；
图6为本发明实施例的对比例1、对比例2、实施例1的发射光谱。
具体实施方式
为使本领域技术人员更好地理解本发明实施例的技术方案，下面结合附图和具体实施方式对本发明实施例作进一步详细描述。
可以理解的是，此处描述的具体实施例和附图仅仅用于解释本发明实施例，而非对本发明的限定。
可以理解的是，在不冲突的情况下，本发明的各实施例及实施例中的各特征可相互组合。
可以理解的是，为便于描述，本发明实施例的附图中仅示出了与本发明实施例相关的部分，而与本发明实施例无关的部分未在附图中示出。
第一方面，本发明实施例提供一种发光器件，其包括阴极、阳极，以及设于阴极和阳极间的第一发光层、第二发光层，所述第一发光层位于第二发光层靠近阳极一侧；其中，
所述第一发光层包括第一主体材料和第一客体材料，所述第一主体材料的空穴迁移率高于电子迁移率；
所述第二发光层包括第二主体材料和第二客体材料，所述第二主体材料的空穴迁移率高于电子迁移率；
S1(h1)>S1(g1)，T1(h1)>T1(g1)，S1(g1)-T1(g1)≤0.1eV；
S1(h2)>S1(g2)，T1(h2)>T1(g2)，S1(g2)-T1(g2)≤0.1eV；
S1(h1)≥S1(h2)>S1(g1)>S1(g2)，T1(h1)≥T1(h2)>T1(g1)>T1(g2)；
其中T1表示三线态激发能量，S1表示单线态激发能量，h1表示第一主体材料，h2表示第二主体材料，g1表示第一客体材料，g2表示第二客体材料；
所述第二客体材料为热活化延迟荧光材料；
所述第一发光层的发射光谱所覆盖区域中，有至少40％的面积与第二发光层的吸收光谱所覆盖区重叠。
参照图1，本发明实施例的发光器件包括阳极(Aonde)、阴极(Cathode)，以及和夹在阴极和阳极之间的第一发光层(EML1)和第二发光层(EML2)，其中第一发光层比第二发光层更靠近阳极。
而两个发光层都分别包括各自的主体材料(第一主体材料、第二主体材料)和客体材料(第一客体材料、第二客体材料)，从而该发光器件是有机发光二极管(OLED)发光器件。
而且，各发光层的各材料，还满足以下的性质：
(1)在每个发光层中，主体材料的空穴迁移率均高于电子迁移率。
(2)在每个发光层中，主体材料的单线态激发能量(S1)和三线态激发能量(T1)均高于客体材料的相应能量；同时，客体材料的S1与T1之间差小于0.1eV(电子伏)，即客体材料的能带差(带隙)ΔE ST很小。
(3)第一发光层的第一主体材料的S1(h1)和T1(h1)，分别大于或等于第二发光层的第二主体材料的S1(h2)和T1(h2)；而第一发光层的第一客体材料的S1(g1)和T1(g1)，分别大于第二发光层的第二客体材料的S1(g2)和T1(g2)；而且，第二发光层的第二主体材料的S1(h2)和T1(h2)，分别大于第一发光层的第一客体材料的S1(g1)和T1(g1)。
(4)至少第二客体材料为热活化延迟荧光(TADF)材料，即能发出热活化延迟荧光的材料。
(5)第一发光层的发射光谱有至少40％是与第二发光层的吸收光谱重合的。即参照图4，第一发光层的发射光谱(横坐标为波长，纵坐标为光强)下方覆盖一定的区域，而第二发光层的吸收光谱下方也覆盖一定的区域，则第一发光层的发射光谱覆盖的区域从面积上看，有至少40％与第二发光层的吸收光谱所覆盖的区域重叠。
可见，两个发光层中的两种主体材料和两种客体材料的能级分布参照图2。
图2中，S0表示基态能量；“电子激发”处的25％和75％，表示根据基本物理原理，电子空穴复合后，有25％的单线态能量和75％的三线态能量。
图2中，以第一主体材料和第二主体材料为相同材料为例，即两种主体材料的T1(h1)和T1(h2)相等，而S1(h1)和S1(h2)也相等。
可见，第一发光层/第二发光层的主体材料的T1(h1)/T1(h2)与第一发光层的客体材料的T1(g1)和第二发光层的客体材料的T1(g2)之间，均分别能发生良好的Dexter能量转移；由此，可使能量传递到两个客体材料的三线态上，再利用TADF材料的反向系统间交叉(RISC)将能量转移到单线态。
同时，由于第一发光层的发射光谱有至少40％与第二发光层的吸收光谱重合，故第一发光层/第二发光层的主体材料的S1(h1)/S1(h2)与第一发光层的客体材料的S1(g1)和第二发光层的客体材料的S1(g2)之间，以及第一发光层的客体材料的S1(g1)和第二发光层的客体材料的S1(g2)之间，均可分别发生良好的Forster能量转移；这表明，第一发 光层可向第二发光层进行高效的Forster能量传递。
可见，在本发明实施例的双发光层结构中，第一发光层和第二发光层中电子空穴都能复合形成激子，但主要(或全部)由第二发光层进行发光，从而一定程度上实现发光中心与复合中心的分离，减少非辐射效应，提高器件稳定性；同时，以上结构可实现多种渠道的能量转移，从而实现三线态激子的高效利用，降低自身淬灭，提升发光效率；而且，以上两个发光层只要符合简单的能级和光谱要求即可，故可选的材料范围广，不存在材料开发困难的问题。
可选的，第二客体材料的发射光谱的半峰全宽(FWHM)小于或等于35nm。
如前，本发明实施例的发光器件主要依靠第二客体材料发光，故第二客体材料的发射光谱应当较窄，以使其发光的颜色“更纯”，进一步改善色域。
可选的，发光器件发出的光中，由第一客体材料发出的光的能量的占比小于20％。
如前，本发明实施例的发光器件中，通过将能量转移到第二发光层后，主要由第二发光层(第二客体材料)发光，故其中第一客体材料发出的光在发光器件最终整体的出光中的占比应当尽量的少。
可选的，第一发光层中，第一主体材料的质量百分含量在60％至95％之间，第一客体材料的质量百分含量在5％至40％之间；
可选的，第二发光层中，第二主体材料的质量百分含量在70％至99％之间，第二客体材料的质量百分含量在1％至30％之间。
在第一发光层中，第一主体材料的质量百分含量可在60％至95％之间，进一步在70％至90％之间，更进一步在75％至85％之间；而第一客体材料的质量百分含量可在5％至40％之间，进一步在10％至30％之间，更进一步在15％至25％之间。
在第二发光层中，第二主体材料的的质量百分含量在70％至99％ 之间，进一步在80％至95％之间，更进一步在85％至90％之间；而第二客体材料的质量百分含量在1％至30％之间，进一步在5％至20％之间，更进一步在10％至15％之间。
其中，“在A中，B的质量百分含量”是指，B是A的一部分，当以A的整体(包括B)的质量为100％时，B质量的相对百分比。
可选的，第一主体材料、第一客体材料、第二主体材料中的至少一者为热活化延迟荧光材料。
作为本发明实施例的一种方式，第一主体材料、第一客体材料、第二主体材料中，也可有一者或多者为TADF材料，以进一步提高发光效率。
可选的，第一主体材料和第二主体材料为相同的材料。
作为本发明实施例的一种方式，为了简便，第一主体材料与第二主体材料可以是完全相同材料。
可选的，第一发光层的厚度在5nm至15nm之间。
可选的，第二发光层的厚度在1nm至20nm之间。
第一发光层的厚度可在5nm至15nm之间，进一步可8nm至12nm之间。
第二发光层的厚度可在1nm至20nm之间，进一步可5nm至15nm之间。
可选的，发光器件还包括以下结构的至少一种：
空穴注入层、空穴传输层、空穴阻挡层、电子注入层、电子传输层、电子阻挡层、覆盖层、封装层。
在本发明实施例的发光器件中，还可包括其它的层结构，而这些层结构如果存在，则应位于自身的相应位置。
例如，参照图3，发光器件的阳极设于基底上，而从阳极开始，沿逐渐远离基底的方向，发光器件可依次包括：阳极(Aonde)、空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)、第一发光层(EML1)、第二发光层(EML2)、空穴阻挡层(HBL)、电子 传输层(ETL)、电子注入层(EIL)、阴极(Cathode)、覆盖层(CPL，Capping Layer)、封装层(EN)。
其中，阳极(Aonde)为发光器件的“正极”，可为具有高功函数的材料；当光从阳极侧射出(如发光器件采用底发射结构)时，阳极可采用透明氧化物ITO(氧化铟锡)、IZO(氧化锌锡)等，厚度可在80～200nm；而当光从阴极侧射出(如发光器件采用顶发射结构)时，阳极可采用金属与透明氧化物层的复合结构，如“Ag(银)/ITO”或“Ag/IZO”等，其中金属层厚度可在80nm～100nm，金属氧化物测部分厚度可在5nm～10nm，使阳极整体的反射率参考值达到85％～95％。
空穴注入层(HIL)，其主要作用为降低空穴注入的势垒，提高空穴注入效率，其可为HAT-CN(2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲)、CuPc(酞菁铜)等材料的单层膜，也可通过对空穴传输层的材料进行P型掺杂得到，如为NPB(N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺):F4TCNQ(2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌)、TAPC(4,4'-环己基二[N,N-二(4-甲基苯基)苯胺]):MnO 3(三氧化锰)等，其中掺杂浓度(质量百分含量)可在0.5％～10％；而空穴注入层的厚度可在5nm～20nm。
空穴传输层(HTL)，其主要用于空穴的传输，可采用空穴迁移率较高材料，如咔唑类材料，材料的分子最高被占据轨道(HOMO)能级在-5.2eV～-5.6eV之间，厚度可在100nm～140nm。
电子阻挡层(EBL)，其主要作用是传输空穴而阻挡电子和发光层产生的激子，厚度可在1nm～10nm。
第一发光层(EML1)，即以上的第一发光层，可通过第一主体材料与第一客体材料的共同蒸镀形成。
第二发光层(EML2)，即以上的第二发光层，可通过第二主体材料与第二客体材料的共同蒸镀形成。
空穴阻挡层(HBL)，其主要作用是传输电子而阻挡空穴和发光层产生的激子，厚度可在2nm～10nm。
电子传输层(ETL)，其主要用于传输电子，可采用噻吩类、咪 唑类、吖嗪类衍生物等与喹啉锂共混形成，其中喹啉锂的质量百分含量可30％～70％；电子传输层的厚度可在20nm～70nm。
电子注入层(EIL)，其主要用于提高电子注入效率，可采用LiF(氟化锂)、LiQ(叔丁基锂)、Yb(镱)、Ca(钙)等材料；电子注入层的厚度可在0.5nm～2nm。
阴极(Cathode)，其是发光器件的“负极”，可采用Mg(镁)、Ag(银)、Al(铝)等金属材料，或采用Mg:Ag的合金材料(其中Mg:Ag的质量比可在3:7～1:9)；当光从阴极侧射出(如发光器件采用顶发射结构)时，阴极厚度可在10nm～20nm，当光从阳极侧射出(如发光器件采用底发射结构)时，阴极厚度可在80nm以上，以保证良好的反射率。
覆盖层(CPL)，其具有较高的折射率以调节出光并形成谐振微腔，改善出光颜色；覆盖层对460nm波长的光的折射率应大于1.8，可通过蒸镀的有机小分子材料构成，厚度可在50nm～80nm。
封装层(EN)，其用于将发光器件的其它结构“封闭”起来，以使它们(尤其是发光层)免受外界水、氧等的影响；封装层可采用框胶，也可采用封装薄膜，或可采用有机层和无机层叠置的复合结构。
下面对本发明实施例的发光器件中第一主体材料、第二主体材料、第一客体材料、第二客体材料可采用的具体物质进行描述。
可选的，第一主体材料和第二主体材料分别独立的选自具有以下通式1的材料：
Figure PCTCN2021115907-appb-000009
其中，每个L分别独立的选自单键、取代的C6至C30的亚芳基、未取代的C6至C30的亚芳基中的任意一种；单键是指与L对应的R1直接通过单键与苯环连接，或与L对应的AR1直接通过单键与N(氮)连接；
AR1选自取代的C6至C30的芳基、未取代的C6至C30的芳基、取代的C2至C30的杂环基、未取代的C2至C30的杂环基、取代的C6至C30的芳香胺基、未取代的C6至C30的芳基胺基、取代的C8至C30的含有芳基和杂环基的基团、未取代的C8至C30的含有芳基和杂环基的基团中的任意一种；
每个R1分别独立的选自氢、取代的C1至C20的烷基、未取代的C1至C20的烷基、取代的C6至C30的芳基、未取代的C6至C30的芳基、取代的C2至C30的杂环基、未取代的C2至C30的杂环基、取代的C8至C30的含有芳基和杂环基的基团、未取代的C8至C30的含有芳基和杂环基的基团、取代的腈基、未取代的腈基、取代的异腈基、未取代的异腈基、羟基、硫醇基中的任意一种；与不同L连接的R1之间无连接，或相互连接形成环结构；
AR1和所有的R1中，有至少一个选自咔唑基R(a)、取代的咔唑基R(a)、联亚三苯基R(b)、取代的联亚三苯基R(b)中的任意一种：
R(a)的结构式为：
Figure PCTCN2021115907-appb-000010
R(b)的结构式为：
Figure PCTCN2021115907-appb-000011
作为本发明实施例的一种方式，第一主体材料和第二主体材料都可选用以上通式1的材料，且第一主体材料和第二主体材料的具体材料可以相同或不同。
其中，以上通式1中L-R1链在苯环上的连接方式表示，每个L-R1链可连接在对应的苯环的任意可连接的位置，从而每个苯环上的两个L-R1链可为邻位、对位、间位等任意位置关系。
其中，“与不同L连接的R1之间无连接，或相互连接形成环结构”是指，在每个通式1的分子中，两个不同的L-R1链之间可无直接连接，或者，两个L-R1链的R1之间也可形成连接(前提是两个R1之间能形成连接)，从而形成环状结构。当然，相互连接成环的两个L-R1链通常是“相邻”的，如连接在同一个苯环上，进一步是位于邻位的。
其中，C后边加上数字，表示相应基团中的碳原子的总数；下同。
其中，“基团A为单键”，也可理解为基团A“不存在”，即分别与基团A连接的两个基团，实际上是直接通过单键直接连接的；下同。
其中，“取代的基团A”是指，基团A的氢中，有至少一个被其它的元素或基团取代后形成的基团，例如氢可被卤素、短链(如C1～C5)的烷基、芳基等取代后；下同。相应的，“未取代的基团A”是指基团A的氢中，不能有被其它基团取代的；下同。
其中，基团A为氢元素时，也包括氢的同位素，尤其是为同位素氘(D)，因为氘相对较重，有利于提高分子的稳定性；下同。
其中，“含有芳基和杂环基的基团A”是指，在基团A中，同时含有芳环和杂环，或者说该基团A是芳基和杂环基的“混合”；下同。
可选的，第一客体材料具有以下通式2：
Figure PCTCN2021115907-appb-000012
其中，X1选自C(碳)或N(氮)；
每个R2分别独立的选自基团A、取代的基团A、基团B、取代的基团B中的任意一种，且所有R2中，有至少两个为基团A或取代的基团A，有至少一个为基团B或取代的基团B；
基团A的结构式为以下任意一种：
Figure PCTCN2021115907-appb-000013
其中，X2选自N(氮)、O(氧)、S(硫)中的任意一种；
基团B的结构式为以下任意一种：
Figure PCTCN2021115907-appb-000014
其中，X3选自O(氧)或S(硫)；每个R3分别独立的选自氢、卤素基团、取代的甲硅烷基、未取代的甲硅烷基、腈基、取代的C1至C20的烷基、未取代的C1至C20的烷基、取代的C1至C20的烷氧基、未取代的C1至C20的烷氧基、取代的C6至C30的芳基、未取代的C6至C30的芳基、取代的C2至C30的杂环基、未取代的C2至C30的杂环基中的任意一种。
其中，以上R3为取代的烷基或取代的烷氧基时，其氢优选被卤素取代，即其可为卤代烷基或卤代烷氧基；进一步的，卤代烷基或卤代烷氧基中如果还有氢，则这些氢还可被其它非卤素的基团取代，即可为取代的卤代烷基或取代的卤代烷氧基。
可选的，第二客体材料具有以下通式3：
Figure PCTCN2021115907-appb-000015
其中，每个R4分别独立的选自氢、卤素基团、取代的甲硅烷基、未取代的甲硅烷基、腈基、取代的C1至C20的烷基、未取代的C1至C20的烷基、取代的C1至C20的烷氧基、未取代的C1至C20的烷氧基、取代的C6至C30的芳基、未取代的C6至C30的芳基、取代的C2至C30的杂环基、未取代的C2至C30的杂环基中的任意一种；
每个X4分别独立的选自单键、O(氧)、S(硫)、N(氮)-R5中的任意一种；单键是指与X4连接的两个苯环直接通过单键连接；R5选自氢、卤素基团、取代的甲硅烷基、未取代的甲硅烷基、腈基、取代的C1至C20的烷基、未取代的C1至C20的烷基、取代的C1至C20的烷氧基、未取代的C1至C20的烷氧基、取代的C6至C30的芳基、未取代的C6至C30的芳基、取代的C2至C30的杂环基、未取代的C2至C30的杂环基中的任意一种。
其中，以上R4为取代的烷基或取代的烷氧基时，其氢优选被卤素取代，即其可为卤代烷基或卤代烷氧基；进一步的，卤代烷基或卤代烷氧基中如果还有氢，则这些氢还可被其它非卤素的基团取代，即可为取代的卤代烷基或取代的卤代烷氧基。
进一步的，本发明实施例还采用市售的材料，分别制备了现有技术的发光器件(对比例1和对比例2)和本发明实施例的发光器件(实施例1)，它们的结构具体如下：
对比例1(底发射结构)：
Aonde(ITO)(70nm)/HIL(市售材料)(10nm)/HTL(市售材 料)(160nm)/EBL(市售材料)(10nm)/EML(75％市售主体材料:25％市售TADF材料)(25nm)/HBL(市售材料)(5nm)/ETL(市售材料)(40nm)/EIL(市售材料)(1nm)/Cathode(80％Mg:20％Ag)(160nm)。
对比例2(底发射结构)：
Aonde(ITO)(70nm)/HIL(市售材料)(10nm)/HTL(市售材料)(160nm)/EBL(市售材料)(10nm)/EML(75％市售主体材料:24％市售TADF材料:1％市售的非TADF的常规荧光材料)(25nm)/HBL(市售材料)(5nm)/ETL(市售材料)(40nm)/EIL(市售材料)(1nm)/Cathode(80％Mg:20％Ag)(160nm)。
实施例1(参照图3的底发射结构)：
Aonde(ITO)(70nm)/HIL(市售材料)(10nm)/HTL(市售材料)(160nm)/EBL(市售材料)(10nm)/EML1(80％市售第一主体材料:20％市售第一客体材料)(10nm)/EML1(75％市售第二主体材料:25％市售第二客体材料)(15nm)/HBL(市售材料)(5nm)/ETL(市售材料)(40nm)/EIL(市售材料)(1nm)/Cathode(80％Mg:20％Ag)(160nm)。
其中，EML表示对比例中的单独的一个发光层.
其中，每个结构后的第一个括号表示结构采用的材料，若为多种材料的混合，则百分比表示相应材料的质量百分含量；结构后的第二个括号表示结构的厚度。
其中，实施例1中使用的第一主体材料和第二主体材料是相同的，且与对比例1和对比例2中发光层的主体材料相同。
其中，实施例1中使用的第一主体材料/第二主体材料(二者相同)、第一客体材料、第二客体材料的能级如下表：
表1、实施例1中使用的材料的参数
Figure PCTCN2021115907-appb-000016
Figure PCTCN2021115907-appb-000017
可见，以上各材料的能级，符合本发明实施例的要求。
其中，实施例1中第一发光层的发射光谱和第二发光层的吸收光谱参照图4，可见其符合“第一发光层的发射光谱所覆盖区域中，有至少40％的面积与第二发光层的吸收光谱所覆盖区重叠”的要求。
其中，实施例1中第一客体材料的发射光谱和发光器件的发射光谱参照图5。可见，在对应第一客体材料的发射光谱的主峰峰值处，发光器件的发射光谱完全为平线(即在该波长处发光器件不发光)。这表明，发光器件发出的光中，完全没有来自第一客体材料的成分，即发光器件发出的光中，由第一客体材料发出的光的能量的占比为0％(当然符合“小于20％”的要求)。
由此可见，实施例1中发光器件采用的各材料的各项性能，符合本发明实施例的要求。
分别测试对比例1、对比例2、实施例1的发光器件，在15mA/cm 2的电流密度下的电压、发光效率、色坐标(CIE1931色彩空间的色坐标)、半峰全宽(FWHM)、使用寿命(LT95，发光亮度降低到初始的95％的耗时)，结果如下表：
表2、实施例和对比例的性能对比
编号 电压 发光效率 色坐标 FWHM FWHM
对比例1 100％ 100％ (0.31，0.61) 63nm 100％
对比例2 98％ 97％ (0.24，0.70) 30nm 110％
实施例1 99％ 113％ (0.19，0.76) 26nm 88％
其中，所有百分比的数据表示，以对比例1的测试值为100％时，其它对比例和实施例的测试结果的相对百分比。
分别测试对比例1、对比例2、实施例1的发光器件的发光光谱，结果参照图6。
从以上结果可见，实施例1的发光器件的发光效率明显高于各对比例，而半峰全宽则明显低于各对比例。
这表明，本发明实施例的发光器件的发光效率更高，可更充分的 利用能量，且发光光谱窄，色域更好。
第二方面，本发明实施例提供一种显示基板，其包括基底和设于基底上的至少一个发光器件；
所有发光器件中，有至少一个发光器件为上述的发光器件。
可在一个基底上设置多个以上的发光器件，并通过分别控制这些发光器件以所需亮度发光，得到能显示图像的显示基板。
显然，由于以上发光器件为有机发光二极管(OLED)发光器件，故本发明实施例的显示基板也是有机发光二极管(OLED)显示基板。
其中，显示基板还可包括栅线、数据线、像素电路(如2T1C像素电路、7T1C像素电路)等用于控制发光器件发光的结构。
其中，显示基板中的发光器件可分为不同颜色，从而实现彩色显示。
第三方面，本发明实施例提供一种显示装置，其包括上述的显示基板。
将上述的显示基板与其它器件(如对盒基板、驱动器件、电源、外壳等)组装在一起，得到能独立使用的显示装置。
具体的，该显示装置可为有机发光二极管(OLED)显示面板、电子纸、手机、平板电脑、电视机、显示器、笔记本电脑、数码相框、导航仪等任何具有显示功能的产品或部件。
可以理解的是，以上实施方式仅仅是为了说明本发明实施例的原理而采用的示例性实施方式，然而本发明并不局限于此。对于本领域内的普通技术人员而言，在不脱离本发明实施例的精神和实质的情况下，可以做出各种变型和改进，这些变型和改进也视为本发明的保护范围。

Claims (14)

  1. 一种发光器件，其特征在于，包括阴极、阳极，以及设于阴极和阳极间的第一发光层、第二发光层，所述第一发光层位于第二发光层靠近阳极一侧；其中，
    所述第一发光层包括第一主体材料和第一客体材料，所述第一主体材料的空穴迁移率高于电子迁移率；
    所述第二发光层包括第二主体材料和第二客体材料，所述第二主体材料的空穴迁移率高于电子迁移率；
    S1(h1)>S1(g1)，T1(h1)>T1(g1)，S1(g1)-T1(g1)≤0.1eV；
    S1(h2)>S1(g2)，T1(h2)>T1(g2)，S1(g2)-T1(g2)≤0.1eV；
    S1(h1)≥S1(h2)>S1(g1)>S1(g2)，T1(h1)≥T1(h2)>T1(g1)>T1(g2)；
    其中T1表示三线态激发能量，S1表示单线态激发能量，h1表示第一主体材料，h2表示第二主体材料，g1表示第一客体材料，g2表示第二客体材料；
    所述第二客体材料为热活化延迟荧光材料；
    所述第一发光层的发射光谱所覆盖区域中，有至少40％的面积与第二发光层的吸收光谱所覆盖区重叠。
  2. 根据权利要求1所述的发光器件，其特征在于，
    所述第二客体材料的发射光谱的半峰全宽小于或等于35nm。
  3. 根据权利要求1所述的发光器件，其特征在于，
    所述发光器件发出的光中，由所述第一客体材料发出的光的能量的占比小于20％。
  4. 根据权利要求1所述的发光器件，其特征在于，
    所述第一发光层中，所述第一主体材料的质量百分含量在60％至95％之间，所述第一客体材料的质量百分含量在5％至40％之间；
  5. 根据权利要求1所述的发光器件，其特征在于，
    所述第二发光层中，所述第二主体材料的质量百分含量在70％至99％之间，所述第二客体材料的质量百分含量在1％至30％之间。
  6. 根据权利要求1所述的发光器件，其特征在于，
    所述第一主体材料、第一客体材料、第二主体材料中的至少一者为热活化延迟荧光材料。
  7. 根据权利要求1所述的发光器件，其特征在于，
    所述第一主体材料和第二主体材料为相同的材料。
  8. 根据权利要求1所述的发光器件，其特征在于，
    所述第一发光层的厚度在5nm至15nm之间。
  9. 根据权利要求1所述的发光器件，其特征在于，
    所述第二发光层的厚度在1nm至20nm之间。
  10. 根据权利要求1所述的发光器件，其特征在于，所述发光器件还包括以下结构的至少一种：
    空穴注入层、空穴传输层、空穴阻挡层、电子注入层、电子传输层、电子阻挡层、覆盖层、封装层。
  11. 根据权利要求1所述的发光器件，其特征在于，所述第一主 体材料和第二主体材料分别独立的选自具有以下通式1的材料：
    Figure PCTCN2021115907-appb-100001
    其中，每个L分别独立的选自单键、取代的C6至C30的亚芳基、未取代的C6至C30的亚芳基中的任意一种；所述单键是指与L对应的R1直接通过单键与苯环连接，或与L对应的AR1直接通过单键与N连接；
    AR1选自取代的C6至C30的芳基、未取代的C6至C30的芳基、取代的C2至C30的杂环基、未取代的C2至C30的杂环基、取代的C6至C30的芳香胺基、未取代的C6至C30的芳基胺基、取代的C8至C30的含有芳基和杂环基的基团、未取代的C8至C30的含有芳基和杂环基的基团中的任意一种；
    每个R1分别独立的选自氢、取代的C1至C20的烷基、未取代的C1至C20的烷基、取代的C6至C30的芳基、未取代的C6至C30的芳基、取代的C2至C30的杂环基、未取代的C2至C30的杂环基、取代的C8至C30的含有芳基和杂环基的基团、未取代的C8至C30的含有芳基和杂环基的基团、取代的腈基、未取代的腈基、取代的异腈基、未取代的异腈基、羟基、硫醇基中的任意一种；与不同L连接的R1之间无连接，或相互连接形成环结构；
    AR1和所有的R1中，有至少一个选自咔唑基R(a)、取代的咔唑基R(a)、联亚三苯基R(b)、取代的联亚三苯基R(b)中的任意一种：
    所述R(a)的结构式为：
    Figure PCTCN2021115907-appb-100002
    所述R(b)的结构式为：
    Figure PCTCN2021115907-appb-100003
  12. 根据权利要求1所述的发光器件，其特征在于，所述第一客体材料具有以下通式2：
    Figure PCTCN2021115907-appb-100004
    其中，X1选自C或N；
    每个R2分别独立的选自基团A、取代的基团A、基团B、取代的基团B中的任意一种，且所有R2中，有至少两个为基团A或取代的基团A，有至少一个为基团B或取代的基团B；
    所述基团A的结构式为以下任意一种：
    Figure PCTCN2021115907-appb-100005
    其中，X2选自N、O、S中的任意一种；
    所述基团B的结构式为以下任意一种：
    Figure PCTCN2021115907-appb-100006
    其中，X3选自O或S；每个R3分别独立的选自氢、卤素基团、 取代的甲硅烷基、未取代的甲硅烷基、腈基、取代的C1至C20的烷基、未取代的C1至C20的烷基、取代的C1至C20的烷氧基、未取代的C1至C20的烷氧基、取代的C6至C30的芳基、未取代的C6至C30的芳基、取代的C2至C30的杂环基、未取代的C2至C30的杂环基中的任意一种。
  13. 根据权利要求1所述的发光器件，其特征在于，所述第二客体材料具有以下通式3：
    Figure PCTCN2021115907-appb-100007
    其中，每个R4分别独立的选自氢、卤素基团、取代的甲硅烷基、未取代的甲硅烷基、腈基、取代的C1至C20的烷基、未取代的C1至C20的烷基、取代的C1至C20的烷氧基、未取代的C1至C20的烷氧基、取代的C6至C30的芳基、未取代的C6至C30的芳基、取代的C2至C30的杂环基、未取代的C2至C30的杂环基中的任意一种；
    每个X4分别独立的选自单键、O、S、N-R5中的任意一种；所述单键是指与X4连接的两个苯环直接通过单键连接；R5选自氢、卤素基团、取代的甲硅烷基、未取代的甲硅烷基、腈基、取代的C1至C20的烷基、未取代的C1至C20的烷基、取代的C1至C20的烷氧基、未取代的C1至C20的烷氧基、取代的C6至C30的芳基、未取代的C6至C30的芳基、取代的C2至C30的杂环基、未取代的C2至C30的杂环基中的任意一种。
  14. 一种显示基板，包括基底和设于所述基底上的至少一个发光器件；其特征在于，
    所有所述发光器件中，有至少一个发光器件为权利要求1至13中任意一项所述的发光器件。
PCT/CN2021/115907 2020-10-16 2021-09-01 发光器件、显示基板 WO2022078094A1 (zh)

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