WO2018133836A1 - 一种有机电致发光器件及其制备方法 - Google Patents

一种有机电致发光器件及其制备方法 Download PDF

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WO2018133836A1
WO2018133836A1 PCT/CN2018/073380 CN2018073380W WO2018133836A1 WO 2018133836 A1 WO2018133836 A1 WO 2018133836A1 CN 2018073380 W CN2018073380 W CN 2018073380W WO 2018133836 A1 WO2018133836 A1 WO 2018133836A1
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host material
ring
organic electroluminescent
electroluminescent device
donor
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PCT/CN2018/073380
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English (en)
French (fr)
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李维维
赵菲
闵超
刘嵩
敖伟
刘玉成
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昆山工研院新型平板显示技术中心有限公司
昆山国显光电有限公司
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Priority to KR1020197015666A priority Critical patent/KR102254393B1/ko
Priority to JP2019529234A priority patent/JP6829768B2/ja
Priority to EP18741504.7A priority patent/EP3573118B1/en
Publication of WO2018133836A1 publication Critical patent/WO2018133836A1/zh
Priority to US16/317,491 priority patent/US11158821B2/en

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Definitions

  • the present invention relates to the field of display devices, and in particular, to an organic electroluminescent device and a method for fabricating the same.
  • the organic electroluminescent device is a self-luminous device, and has been widely concerned as a next-generation flat panel display device due to its wide viewing angle, high contrast, high luminance, low driving voltage, fast response time, and thin and light panel.
  • the luminescence mechanism of the organic electroluminescence device belongs to a carrier injection type, that is, a voltage is applied to the luminescent layer sandwiched between the anode and the cathode, and holes injected from the anode flow through the hole transport layer to move toward the luminescent layer from the cathode.
  • the injected electrons flow through the electron transport layer to the light emitting layer.
  • the holes and electrons as carriers are combined in the light-emitting layer to excite the luminescent substance, and emit light when the excited state is relaxed to the ground state.
  • studies have shown that the electron mobility of the electron transport layer is much lower than the hole mobility of the hole transport layer, which leads to the imbalance of positive carrier transport, which seriously affects the luminous efficiency of the organic electroluminescent device. And service life.
  • the light-emitting layer of the top-emitting organic electroluminescent device generally uses a partial electron-type (acceptable electron) host material and a hole-shaped hole-type (electron-donating) body.
  • a bi-composite material in which the materials are mixed.
  • two materials are commonly used for vapor deposition, but the two materials are separately placed in two evaporation sources for evaporation, which requires high mass production process and affects the yield of mass production.
  • the common electronic type body BAlq or the hole type body CBP is used as the main body, the carrier cannot be balanced, and the luminous efficiency of the device is lowered.
  • an embodiment of the present invention provides an organic electroluminescent device and a method for fabricating the same, wherein a host material of a light-emitting layer of the organic electroluminescent device is disposed in the same evaporation source from a donor host material and a receptor host material. Evaporation to form an exciplex, which solves the technical problems of low luminous efficiency, short service life or complicated operation process of the organic electroluminescent device in the prior art.
  • An organic electroluminescent device includes an anode, a cathode and a light-emitting layer disposed between the anode and the cathode, the host material of the light-emitting layer being composed of a donor body material and a receptor body material Premixing is formed, and the donor host material and the acceptor host material are co-evaporated in the same evaporation source to form an exciplex, and the host material is doped with a guest material.
  • the host material of the light-emitting layer is co-evaporated by the donor host material and the acceptor host material in the same evaporation source to form an exciplex, which is beneficial to electrons and holes.
  • the balance between the streams improves the life and efficiency of the device, and single-source evaporation reduces the difficulty of process operation and improves the yield of mass production.
  • the two host materials form an exciplex, and the excimer is used as a medium to efficiently transfer the triplet energy to the guest material through FRET energy transfer, thereby suppressing the deactivation of the excitation energy and effectively solving the high
  • the problem of a serious roll-off drop in brightness further improves the stability of the device while reducing the doping concentration of the guest material, thereby reducing the product cost.
  • FIG. 1 is a schematic structural view of an organic electroluminescent device according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram of energy transfer of an illuminating layer of an organic electroluminescent device according to an embodiment of the invention.
  • FIG. 3 is a schematic structural view of an organic electroluminescent device according to another embodiment of the present invention.
  • the organic electroluminescent device includes a substrate 10 on which an anode 20 is disposed, and a hole injection layer (HIL) 40, a hole transport layer (HTL) 50, and a light are sequentially stacked on the anode 20.
  • the host material of the luminescent layer 60 is formed by premixing the donor host material and the acceptor host material, and the donor host material and the acceptor host material are co-evaporated in the same evaporation source to form an exciplex, the host material. It is doped with a guest material.
  • the guest material is preferably a phosphorescent material, i.e., the phosphorescent material is dispersed as a guest material in the dual host material, which allows the light emitting device to have high luminous efficiency.
  • the donor body and the acceptor body belong to different series of derivatives, wherein the donor body is selected as a hole-shaped hole-type material, such as an ammonia compound, and the acceptor body is selected as a partial bias.
  • Electronic electronic materials such as phosphorus compounds. Both evaporation temperatures are from 150 ° C to 500 ° C, and the glass transition temperature T g is greater than 100 ° C.
  • the absolute difference between the vapor deposition temperature of the donor body and the acceptor body is less than 30 ° C. In a preferred embodiment, the difference between the vapor deposition temperature of the donor body and the acceptor body is The absolute value is less than 15 ° C. In a more preferred embodiment, the difference in evaporation temperature between the two is less than 5 ° C.
  • the evaporation temperature and the glass transition temperature of the donor body and the acceptor body are in the same range, and the smaller the vapor deposition temperature difference between the two, the more favorable it is to place it in the same evaporation source for co-evaporation (ie, single Source evaporation), which not only facilitates the balance between electrons and hole carriers, but also improves the life and efficiency of the device, and single-source evaporation reduces the difficulty of process operation and improves the yield of mass production.
  • co-evaporation ie, single Source evaporation
  • the donor body and the acceptor body form an exciplex during co-evaporation into a thin film.
  • the triplet energy level of the donor body is greater than the singlet energy level of the exciplex,
  • the energy gap is ⁇ 0.2eV, and the absolute value of the HOMO energy level of the donor body is ⁇ 5.3eV;
  • the triplet energy level of the acceptor body is greater than the singlet energy level of the exciplex, and the energy gap of the two is >0.2eV, and
  • the absolute value of the LUMO level of the acceptor body is > 2.0 eV. That is, in the host material of the embodiment of the present invention, the energy level relationship between the Donor Host and the acceptor host and the exciplex formed by the host material satisfies the following conditions:
  • the exciplex formed is a thermally activated delayed fluorescent exciplex (TADF exciplex), which is a first singlet state and A material having a small energy level difference ( ⁇ EST ⁇ 0.3 eV) between the first three-line states has a heat-activated delayed fluorescence effect.
  • TADF exciplex thermally activated delayed fluorescent exciplex
  • the triplet energy is transferred to the singlet state through the anti-system, and then The energy is transferred to the phosphorescent material; at the same time, the energy of the phosphorescent material itself is also shifted from the singlet state to the triplet state.
  • the triplet energy of the host material and the guest material in the device are efficiently transferred to the phosphorescent material to be fully utilized, thereby improving the device efficiency; and the thermal activation delaying fluorescence fast energy conversion process suppresses the deactivation of the excitation energy ( Light-emitting or heat-deactivation) effectively solves the problem of serious roll-off drop under high brightness, further improving the stability of the device and prolonging the life of the light-emitting device.
  • the short-range Dexter energy transfer is performed in the existing phosphorescent system, it is necessary to increase the doping concentration of the phosphorescent material to ensure sufficient energy transfer.
  • the illuminating device provided by the embodiment of the invention passes the long-range Energy transfer can reduce the doping concentration of the phosphorescent material, thereby reducing product cost.
  • the molecular formula is:
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 substituents are the same or different and are each independently selected from an arylene group or a heteroarylene group (a hetero atom specifically refers to a nitrogen atom);
  • R 1 , R 2 , R 3 and R 4 are Wherein, Ar 5 , A, Ar 6 , B and Ar 7 are connected in a fused ring manner, sharing 2 atoms, and Ar 5 , Ar 6 and Ar 7 are the same or different, and are each independently selected from a benzene ring and a substituted benzene ring.
  • a naphthalene ring a substituted naphthalene ring, an anthracene ring or a substituted anthracene ring
  • A is a five-membered heterocyclic ring or a six-membered heterocyclic ring containing a N atom
  • B is a five-membered ring, a five-membered heterocyclic ring, a six-membered ring or a six-membered ring.
  • Heterocyclic ring (a hetero atom is one or both of a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom).
  • the molecular formula is:
  • X 1 and X 2 are the same or different and are respectively -CH- or -N-;
  • Y is -O-, -S-, -Se-, -C(CH 3 ) 2 -, -C(C 6 H 5 ) 2 - or -C(9-fluorenyl)-;
  • the Ar 8 and Ar 9 substituents are the same or different and are each independently selected from an arylene group or a heteroarylene group (a hetero atom specifically refers to a nitrogen atom);
  • R 5 and R 6 are Wherein Ar 10 , C ring, Ar 11 , D ring and Ar 12 are connected in a fused ring manner, sharing 2 atoms, and Ar 10 , Ar 11 and Ar 12 are the same or different, and are each independently selected from a benzene ring and a substituted one.
  • a benzene ring, a naphthalene ring or a substituted naphthalene ring the C ring is a five-membered heterocyclic ring or a six-membered heterocyclic ring containing a N atom
  • the D ring is a five-membered ring, a five-membered heterocyclic ring, a six-membered ring or a six-membered heterocyclic ring.
  • the atom is a nitrogen atom, an oxygen atom, a sulfur atom, or a selenium atom, and may contain two kinds of hetero atoms at the same time.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 heterocyclic rings are each independently selected from one of the following molecular structures:
  • the donor host material is a compound having the structure:
  • the acceptor host material is a compound having the structure:
  • the optimum carrier balance can be achieved by setting the mixing ratio of the two, in which the equilibrium condition is achieved.
  • the composite probability of holes and electrons in the light-emitting layer 60 is increased and the light-emitting efficiency is improved.
  • the doping mass ratio of the donor body and the acceptor body is from 1:9 to 9:1.
  • a phosphorescent material in an embodiment of the present invention, it is preferably an organometallic complex, and particularly preferably a ruthenium complex such as tris(2-p-tolylpyridine) ruthenium (III) (abbreviation: Ir(mppy) 3 Or bis(2-phenylpyridine) acetylacetonate (III) (abbreviation: [Ir(ppy) 2 (acac)))).
  • ruthenium complex such as tris(2-p-tolylpyridine) ruthenium (III) (abbreviation: Ir(mppy) 3 Or bis(2-phenylpyridine) acetylacetonate (III) (abbreviation: [Ir(ppy) 2 (acac))).
  • an optical compensation layer 90 is disposed between the hole transport layer 50 and the light-emitting layer 60.
  • the material of the optical compensation layer 90 is an electron blocking material having high hole mobility, and the triplet energy level of the electron blocking material is greater than that of the premixed donor host material and the acceptor host material.
  • the triplet energy level of the base complex may be a conventional electron blocking material having a triplet energy level T 1 > 2.6 eV, and the material of the present invention is not specifically limited.
  • the organic electroluminescent device provided by the embodiment of the invention adopts an electron blocking material with a high triplet level as an optical compensation layer, which not only improves the organic electroluminescent device, but also the top, without affecting the driving voltage of the light emitting device.
  • the color purity and efficiency of the organic light-emitting green light-emitting device, and the limitation of electrons in the light-emitting layer region, are advantageous for increasing the recombination probability of the excitons and further improving the luminous efficiency of the device.
  • the optical compensation layer in this embodiment is disposed between the light-emitting layer and the hole transport layer, so that the optical compensation layer and the light-emitting layer can be prepared by using the same set of mask plates during the evaporation process, which can avoid the traditional process due to
  • the problem that the optical compensation layer is disposed between the hole injection layer and the hole transport layer to repeat the alignment of the maskMask improves the process precision and the yield rate to some extent. This is because there is a certain error in each alignment of the mask, so the fewer the number of alignments, the less the error, and the higher the yield of the product.
  • a hole blocking layer (HBL) 100 is disposed between the light emitting layer 60 and the electron transporting layer 70, and may be subjected to a vacuum deposition method, a wet method, a laser transfer method, or the like. The method is formed.
  • HBL material any known hole blocking material such as an oxadiazole derivative, a triazole derivative or a phenanthroline derivative can be used.
  • the hole blocking layer can effectively block hole transport, confine the carrier recombination to the light emitting layer region, and improve the luminous efficiency of the device.
  • the substrate 10 is transparent, and a glass substrate or a flexible substrate made of a compound material such as polyester or polyimide can be used.
  • the anode layer 20 may be an inorganic material or an organic conductive polymer.
  • the inorganic material is generally a metal oxide such as indium tin oxide, zinc oxide or indium zinc oxide or a metal having a higher work function such as gold, copper or silver. Among them, oxidation is preferred.
  • Indium tin (ITO) the organic conductive polymer is preferably one of polythiophene/sodium polyvinylbenzenesulfonate (abbreviation: PEDOT:PSS) and polyaniline (abbreviation: PANI).
  • the cathode layer 30 is generally made of a metal having a lower work function such as lithium, magnesium, calcium, barium, aluminum or indium or an alloy of one of them with copper, gold or silver, or a metal or a metal fluoride, respectively.
  • An electrode layer such as a LiF/Al or Mg:Ag alloy layer/Ag layer.
  • the hole injection layer 40 is a layer containing a substance having a high hole injecting property, and specifically, for example, molybdenum oxide, titanium oxide, vanadium oxide, cerium oxide, cerium oxide, chromium oxide, zirconium oxide, silver oxide, tungsten oxide, manganese oxide, etc. Metal oxide. Further, a phthalocyanine compound such as phthalocyanine (abbreviation: H 2 Pc) or copper phthalocyanine (II) (abbreviation: CuPc) may be selected.
  • the hole transport layer 50 is a layer containing a substance having a high hole transporting property, and specifically, for example, NPB, TPD, BPAFLP, 4,4'-bis[N-(9,9-dimethylindol-2-yl)- N-phenylamino]biphenyl (abbreviation: DFLDPBi) and 4,4'-bis[N-(spirocyclic-9,9'-biindole-2-yl)-N-phenylamino]biphenyl (abbreviation An aromatic amine compound such as BSPB) may also be selected as a carbazole derivative such as CBP, CzPA or PCzPA or an anthracene derivative such as t-BuDNA, DNA or DPAnth.
  • DFLDPBi 4,4'-bis[N-(9,9-dimethylindol-2-yl)- N-phenylamino]biphenyl
  • An aromatic amine compound such as
  • the electron transport layer 70 is a layer containing a substance having a high electron transporting property, and specifically, for example, Alq 3 , tris(4-methyl-8-hydroxyquinoline)aluminum (abbreviation: Almq 3 ), bis(10-hydroxybenzo) Metal complexes such as [h]quinoline) ⁇ (abbreviation: BeBq 2 ), BAlq, Zn(BOX) 2 , bis[2-(2-hydroxyphenyl)benzothiazole]zinc (abbreviation: Zn(BTZ) 2 )
  • Alq 3 tris(4-methyl-8-hydroxyquinoline)aluminum
  • BeBq 2 bis(10-hydroxybenzo) Metal complexes such as [h]quinoline) ⁇
  • BeBq 2 BAlq
  • Zn(BOX) 2 bis[2-(2-hydroxyphenyl)benzothiazole]zinc
  • Zn(BTZ) 2 2-(4-biphenyl)-5-(4-tert-buty
  • the electron injecting layer 80 is a layer containing a substance having a high electron injecting property, and an alkali metal, an alkaline earth metal, and a compound thereof such as lithium, barium, calcium, lithium fluoride, barium fluoride, calcium fluoride, barium fluoride or oxidation may be selected. Lithium, etc.
  • the organic electroluminescent device provided by the present invention will be further illustrated by way of specific examples. However, the invention is not limited to the following embodiments.
  • the host material of the light-emitting layer of the organic electroluminescent device in this embodiment is premixed with the donor host material of different mass ratios and the host material, and the structure of these devices is shown in FIG.
  • the host material of the light-emitting layer 60 is an exciplex (wherein the donor host material is 1-2, the acceptor host material is 2-3, and the donor host material 1-2 and the acceptor host material 2-3 are single source).
  • the evaporation method forms an exciplex, and the phosphorescent material doped in the host material is Ir(mppy)3, and the optical compensation layer 90 is disposed between the hole transport layer 50 and the light-emitting layer 60, and the material has high migration.
  • ITO (20 nm) / hole injection layer (HATCN, 10 nm) / hole transport layer (TCTA, 80 nm) / optical compensation layer (mCBP, 70 nm) / (donor host material (1-2, 10 nm): acceptor body Material (2-3): 10% phosphorescent material Ir (mppy) 3 / electron transport layer (TPBi, 30 nm) / electron injection layer (Bphen, 10 nm) / Mg: Ag (1: 4, 1 nm) / Ag (15 nm)
  • the device structure is as follows:
  • ITO 20 nm
  • hole injection layer HTCN, 10 nm
  • optical compensation layer mCBP, 150 nm
  • mCBP 10% phosphorescent material
  • Ir (mppy) 3 / electron transport layer TPBi, 30 nm
  • Bphen 10 nm
  • Mg Ag (1: 4, 1 nm) / Ag (15 nm)
  • an organic electroluminescent device is prepared, wherein the donor host material is the above-mentioned donor host material 1-24 of the present invention, and the acceptor host material is the above-mentioned acceptor host material 2-10 of the present invention, and the quality of both The ratio is 2:3.
  • the performance of this device is shown in Table 2.
  • Example 1 an organic electroluminescent device is prepared, wherein the donor host material is the above-mentioned donor host material 1-30 of the present invention, and the acceptor host material is the above-mentioned acceptor host material 2-16 of the present invention, and the quality of both The ratio is 2:3, and the performance of the device is shown in Table 2.
  • the embodiment of the invention further provides a method for preparing an organic electroluminescent device, the preparation method comprising: providing an anode on a substrate; and providing a light-emitting layer on the anode, the host material of the light-emitting layer is composed of a donor body material and a receptor body The material is premixed, and the donor host material and the acceptor host material are co-evaporated in the same evaporation source to form an exciplex, the host material is doped with a guest material; and a cathode is disposed on the luminescent layer.
  • the embodiment of the invention effectively solves the problem of serious roll-off drop under high brightness, further improves the stability of the device, and reduces the doping concentration of the guest material, thereby reducing the product cost.
  • the preparation method further includes: sequentially laminating a hole injection layer and a hole transport layer between the anode and the light-emitting layer; and the hole transport layer and the light-emitting layer An optical compensation layer is provided between.
  • a hole injection layer is provided on the anode
  • a hole transport layer is provided on the hole injection layer
  • an optical compensation layer is provided on the hole transport layer, and the optical compensation layer is located under the light-emitting layer.
  • an anode, a hole injection layer, a hole transport layer, an optical compensation layer, a light-emitting layer, a cathode, and the like may be sequentially laminated on a substrate by a conventional vapor deposition or coating process.
  • the organic electroluminescent device of the present invention and the preparation method thereof, the excimer compound is formed by co-evaporating the host material of the light-emitting layer from the donor host material and the acceptor host material in the same evaporation source, which is beneficial to electrons and air.
  • the balance between the carrier carriers increases the lifetime and efficiency of the device, and single-source evaporation reduces the difficulty of process operation and improves the yield of mass production.

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Abstract

一种有机电致发光器件及其制备方法，该有机电致发光器件的发光层（60）的主体材料由供体主体材料和受体主体材料置于同一蒸发源中共蒸镀而形成激基复合物，解决了现有技术中的有机电致发光器件发光效率低、使用寿命短或操作工艺复杂等技术问题。所述的有机电致发光器件，包括阳极（20）、阴极（30）以及设置于阳极（20）和阴极（30）之间的发光层（60），该发光层（60）的主体材料由供体主体材料和受体主体材料预混形成，且供体主体材料和受体主体材料置于同一蒸发源中共蒸镀而形成激基复合物，主体材料中掺杂客体材料。

Description

一种有机电致发光器件及其制备方法
本发明是要求由申请人提出的，申请日为2017年01月20日，申请号为201710048295.3，名称为“一种有机电致发光器件”的申请的优先权。以上申请的全部内容通过整体引用结合于此。
技术领域
本发明涉及显示器件技术领域，具体涉及一种有机电致发光器件及其制备方法。
背景技术
有机电致发光器件是自发光装置，由于其具有宽视角、高对比度、高亮度、低驱动电压、快速的响应时间以及面板轻薄等特性，作为下一代的平板显示器件已受到广泛关注。
有机电致发光器件的发光机理属于载流子注入型，即对夹在阳极和阴极之间的发光层施加电压，则从阳极注入的空穴流经空穴传输层向发光层移动，从阴极注入的电子流经电子传输层向发光层移动。作为载流子的空穴和电子在发光层复合，以使发光物质激发，当该激发态驰豫至基态时发光。然而，经研究表明，电子传输层的电子迁移率远远低于空穴传输层的空穴迁移率，这导致了正负载流子传输的不平衡，严重影响了有机电致发光器件的发光效率和使用寿命。
为了调节发光层载流子的平衡性，顶发光有机电致发光器件的发光层一般会选用偏电子的电子型(接受电子型)主体材料和偏空穴的空穴型(给予电子型)主体材料相混合的双主体材料。现有技术中，通常采用两种材料共蒸镀的方式，但这需要将两种材料分别放入两个蒸发源中进行蒸镀，对量产工艺要求高，影响了量产的良率。但若采用常见的电子型主体BAlq或空穴型主体CBP单独作为主体，又都无法使载流子平衡，降低了器件的发光效率。
为了解决上述问题，业界内研究出一种采用双极性单一主体材料的方法，虽然此种发光材料的有机电致发光器件在一定程度上能够调整载流子的平衡，但是一般效率仍较低，寿命尚需提高，roll-off较为严重的问题也需要解决。
发明内容
有鉴于此，本发明实施例提供了一种有机电致发光器件及其制备方法，该有机电致发光器件的发光层的主体材料由供体主体材料和受体主体材料置于同一蒸发源中共蒸镀而形成激基复合物，解决了现有技术中的有机电致发光器件发光效率低、使用寿命短或操作工艺复杂等技术问题。
本发明一实施例提供的一种有机电致发光器件，包括阳极、阴极以及设置于所述阳极和阴极之间的发光层，所述发光层的主体材料由供体主体材料和受体主体材料预混形成，且所述供体主体材料和受体主体材料置于同一蒸发源中共蒸镀而形成激基复合物，所述主体材料中掺杂客体材料。
本发明实施例提供的有机电致发光器件，其发光层的主体材料由供体主体材料和受体主体材料置于同一蒸发源中共蒸镀而形成激基复合物，不仅利于电子与空穴载流子间的平衡，提升了器件的寿命和效率，而且单源蒸镀降低了工艺操作难度，提高了量产的良率。另外，两主体材料形成激基复合物，并以该激基复合物为介质，通过FRET能量传递，将三线态能量高效地转移给客体材料，抑制了激发能量的失活，有效地解决了高亮度下roll-off下降严重的问题，使得器件的稳定性进一步提高，同时减少了客体材料的掺杂浓度，从而降低了产品成本。
附图说明
图1所示为本发明一实施例提供的一种有机电致发光器件的结构示意图。
图2所示为本发明一实施例提供的一种有机电致发光器件发光层能量传递示意图。
图3所示为本发明另一实施例提供的一种有机电致发光器件的结构示意图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
图1所示为本发明一实施例提供的在阳极和阴极间设置有发光层的有机电致发光器件。如图1所示，该有机电致发光器件包括基板10，基板10上设置有阳极20，阳极20上依次层叠设置有空穴注入层(HIL)40、空穴传输层(HTL)50、发光层60、电子传输层(ETL)70、电子注入层(EIL)80，透明阴极30。
发光层60的主体材料是由供体主体材料和受体主体材料预混形成的，且供体主体材料和受体主体材料被置于同一蒸发源中共蒸镀而形成激基复合物，主体材料中掺杂有客体材料。在一实施例中，客体材料优选为磷光材料，即磷光材料作为客体材料分散在双主体材料中，其可使发光器件具有高的发光效率。
在本发明一实施例中，该供体主体和受体主体属于不同系列的衍生物，其中，供体主体选为偏空穴的空穴型材料，如氨类化合物，受体主体选为偏电子的电子型材料，如磷类化合物。二者的蒸发温度均为150℃～500℃，玻璃转化温度T g均大于100℃。
在本发明一实施例中，该供体主体和受体主体蒸镀温度的差值绝对值小于30℃，在一优选的实施例中，该供体主体和受体主体蒸镀温度的差值绝对值小于15℃，在一更优的实施例中，二者蒸镀温度的差值绝对值小于5℃。即供体主体和受体主体的蒸发温度和玻璃转化温度在同一范围内，二者间的蒸镀温度差值越小，越有利于将其置于同一蒸发源中进行共蒸镀(即单源蒸镀)，从而不仅可以利于电子与空穴载流子间的平衡，提升器件的寿命和效率，而且单源蒸镀降低了工艺操作难度，提高了量产的良率。
供体主体和受体主体在共蒸镀成薄膜时形成激基复合物，在本发明一实施例中，该供体主体的三线态能级大于激基复合物的单线态能级，二者的能隙≥0.2eV，且供体主体的HOMO能级绝对值≤5.3eV；受体主体的三线态能级大于激基复合物的单线态能级，二者的能隙>0.2eV，且受体主体的LUMO能级绝对值>2.0eV。即本发明实施例的主体材料中供体主体(Donor Host)和受体主体(Acceptor Host)，与其形成的激基复合物间的能级关系满足下面条件：
Figure PCTCN2018073380-appb-000001
Figure PCTCN2018073380-appb-000002
│HOMOD│≤5.3eV
│LUMOA│>2.0eV
其中
Figure PCTCN2018073380-appb-000003
表示供体的三线态能级，
Figure PCTCN2018073380-appb-000004
表示受体的三线态能级，S 1表示激基复合物的单线态能级，HOMO D表示供体的HOMO能级，LUMO A表示受体的LUMO能级。
当两种主体材料满足上述4项条件后，其形成的激基复合物为热激活延迟荧光激基复合物(TADF激基复合物)，这种激基复合物是一种第一单线态和第一三线态之间能级差较小(△EST<0.3eV)的材料，具有热活化延迟荧光效应。
如图2所示，本发明实施例双主体形成的TADF激基复合物，其三线态能量经反系间窜跃转移给了单线态，然后经
Figure PCTCN2018073380-appb-000005
能量传递给了磷光材料；同时，磷光材料自身的能量也从单线态转向了 三线态。这样一来，器件中主体材料和客体材料的三线态能量都高效地转移到了磷光材料而得到充分利用，提升了器件效率；且热激活延迟荧光快速的能量转换过程抑制了激发能量的失活(发光或热失活)，有效地解决了高亮度下roll-off下降严重的问题，使得器件的稳定性进一步提高，延长了发光器件的寿命。另外，因为现有的磷光体系中进行的是短程Dexter能量转移，需要提高磷光材料的掺杂浓度才能保证充分的能量转移。而本发明实施例提供的发光器件通过长程的
Figure PCTCN2018073380-appb-000006
能量转移可以减少磷光材料的掺杂浓度，从而降低了产品成本。
作为供体主体材料，在本发明一实施例中，其分子通式为：
Figure PCTCN2018073380-appb-000007
式中，Ar 1、Ar 2、Ar 3和Ar 4取代基相同或不同，分别独立选自亚芳基或亚杂芳基(杂原子特指氮原子)；
R 1、R 2、R 3和R 4的结构为
Figure PCTCN2018073380-appb-000008
其中，Ar 5、A、Ar 6、B和Ar 7是以稠环方式连接的，共用2个原子，Ar 5、Ar 6和Ar 7相同或不同，分别独立选自苯环、取代的苯环、萘环、取代的萘环、蒽环或取代的蒽环，A为含N原子的五元杂环或六元杂环，B为五元环、五元杂环、六元环或六元杂环(杂原子为氮原子、氧原子、硫原子或硒原子中的一种或两种)。
作为受体主体材料，在本发明一实施例中，其分子通式为：
Figure PCTCN2018073380-appb-000009
式中，X 1和X 2相同或不同，分别为-CH-或-N-；
Y为-O-、-S-、-Se-、-C(CH 3) 2-、-C(C 6H 5) 2-或-C(9-芴基)-；
Ar 8和Ar 9取代基相同或不同，分别独立选自亚芳基或亚杂芳基(杂原子特指氮原子)；
R 5和R 6的结构为
Figure PCTCN2018073380-appb-000010
其中，Ar 10、C环、Ar 11、D环和Ar 12是以稠环方式连接的，共用2个原子，Ar 10、Ar 11和Ar 12相同或不同，分别独立选自苯环、取代的苯环、萘环或取代的萘环，C环为含N原子的五元杂环或六元杂环，D环为五元环、五元杂环、六元环或六元杂环(杂原子为氮原子、氧原子、硫原子、硒原子，可以同时含有两种杂原子)。
优选地，R 1、R 2、R 3、R 4、R 5和R 6杂环分别独立选自以下任意分子结构中的一种：
Figure PCTCN2018073380-appb-000011
Figure PCTCN2018073380-appb-000012
进一步优选地，供体主体材料为具有如下结构的化合物：
Figure PCTCN2018073380-appb-000013
Figure PCTCN2018073380-appb-000014
Figure PCTCN2018073380-appb-000015
Figure PCTCN2018073380-appb-000016
优选地，受体主体材料为具有如下结构的化合物：
Figure PCTCN2018073380-appb-000017
Figure PCTCN2018073380-appb-000018
Figure PCTCN2018073380-appb-000019
在将容易给予电子的化合物及容易接受电子的化合物分别用作供体主体材料和受体主体材料时，可以通过设定二者的混合比率来达到最佳的载流子平衡，在该平衡条件下使发光层60内的空穴和电子的复合概率提高且发光效率提高。在本发明一实施例中，供体主体和受体主体的掺杂质量比为1:9～9:1。
作为磷光材料，在本发明一实施例中，其优选为有机金属配合物，尤其优选为铱配合物，例如三(2-对甲苯基吡啶)合铱(Ⅲ)(缩写：Ir(mppy) 3)或乙酰丙酮酸二(2-苯基吡啶)合铱(Ⅲ)(缩写：[Ir(ppy) 2(acac)])等。
在本发明一实施例中，如图3所示，空穴传输层50和发光层60之间设置有光学补偿层90。在一实施例中，光学补偿层90的材料为具有高空穴迁移率的电子阻挡材料，且该电子阻挡材料的三线态能级大于预混的供体主体材料和受体主体材料所形成的激基复合物的三线态能级。在本发明一实施例中，该光学补偿层90的材料为其三线态能级T 1>2.6eV的常规电子阻挡材料即可，本发明对其材料不做具体限定。
本发明实施例提供的有机电致发光器件，采用高三线态能级的电子阻挡材料作为光学补偿层，不仅在不影响发光器件驱动电压的情况下，提高了有机电致发光器件，尤其是顶发光有机电致绿光器件的色纯度和效率，而且将电子局限在发光层区域，有利于提高激子的复合几率，进一步提高了器件的发光效率。另外，该实施例中的光学补偿层设置于发光层和空穴传输层之间，使得光学补偿层和发光层在蒸镀过程中，可采用同一组掩膜板制备，能够避免传统工艺中由于将光学补偿层设置于空穴注入层和空穴传输层之间所导致的掩膜板Mask重复对位的问题，在一定程度上提高了工艺精度和良品率。这是由于掩膜板的每次对位都会有一定误差，因此对位次数越少，误差就越少，产品良率也就相应地提高。
在本发明另一实施例中，如图3所示，发光层60和电子传输层70间设置有空穴阻挡层(HBL)100，其可通过真空沉积法、湿法或激光转印法等方法形成。作为HBL材料，可以采用任何一种已知的空穴阻挡材料，例如噁二唑衍生物、三唑衍生物或菲咯啉衍生物等。空穴阻挡层可以有效地阻挡空穴传输，将载流子复合限制在发光层区域，提高了器件的发光效率。
基板10为透明的，可以采用玻璃基片或者由聚酯类、聚酰亚胺类等化合物材料构成的柔性基片。
阳极层20可采用无机材料或有机导电聚合物，无机材料一般为氧化铟锡、氧化锌、氧化铟锌等金属氧化物或金、铜、银等功函数较高的金属，其中，优选为氧化铟锡(ITO)，有机导电聚合物优选为聚噻吩/聚乙烯基苯磺酸钠(缩写：PEDOT:PSS)、聚苯胺(缩写：PANI)中的一种材料。
阴极层30一般采用锂、镁、钙、锶、铝或铟等功函数较低的金属或它们中的一种与铜、金或银的合金，或上述金属分别与合金或金属氟化物形成的电极层，例如LiF/Al或Mg:Ag合金层/Ag层。
空穴注入层40为包含具有高空穴注入性物质的层，具体可选择如氧化钼、氧化钛、氧化钒、氧化铼、氧化钌、氧化铬、氧化锆、氧化银、氧化钨和氧化锰等金属氧化物。此外，还可选择如酞菁(缩写：H 2Pc)或酞菁铜(Ⅱ)(缩写：CuPc)等酞菁类化合物。
空穴传输层50为包含具有高空穴传输性物质的层，具体可选择如NPB、TPD、BPAFLP、4,4’-双[N-(9,9-二甲基芴-2-基)-N-苯基氨基]联苯(缩写：DFLDPBi)和4,4’-双[N-(螺环-9,9’-联芴-2-基)-N-苯基氨基]联苯(缩写：BSPB)等芳族胺化合物，还可选择如CBP、CzPA、PCzPA等咔唑衍生物或如t-BuDNA、DNA、DPAnth等蒽衍生物。
电子传输层70为包含具有高电子传输性物质的层，具体可选择如Alq 3、三(4-甲基-8-羟基喹 啉)铝(缩写：Almq 3)、双(10-羟基苯并[h]喹啉)铍(缩写：BeBq 2)、BAlq、Zn(BOX) 2、双[2-(2-羟基苯基)苯并噻唑]锌(缩写：Zn(BTZ) 2)等金属配合物，也可选择如2-(4-联苯基)-5-(4-叔丁基苯基)-1,3,4-噁二唑(缩写：PBD)、1,3-双[5-(对叔丁基苯基)-1,3,4-噁二唑-2-基]苯(缩写：OXD-7)、3-(4-叔丁基苯基)-4-苯基-5-(4-联苯基)-1,2,4-三唑(缩写：TAZ)、3-(4-叔丁基苯基)-4-(4-乙基苯基)-5-(4-联苯基)-1,2,4-三唑(缩写：p-EtTAZ)、红菲绕啉(缩写：BPhen)等杂芳族化合物。
电子注入层80为包含具有高电子注入性物质的层，可选择碱金属、碱土金属和其化合物，如锂、铯、钙、氟化锂、氟化铯、氟化钙、氟化铒或者氧化锂等。下面将通过具体实施例进一步说明本发明提供的有机电致发光器件。但是，本发明并不局限于下列实施例。
实施例1
本实施例中的有机电致发光器件发光层的主体材料由不同质量比的供体主体材料与受体主体材料预混而成，这些器件的结构如图3所示。发光层60的主体材料为激基复合物(其中，供体主体材料为1-2，受体主体材料为2-3，供体主体材料1-2和受体主体材料2-3采用单源蒸镀的方式形成激基复合物)，主体材料中掺杂的磷光材料为Ir(mppy)3，光学补偿层90设置于空穴传输层50和发光层60之间，其材料为具有高迁移率的电子阻挡材料mCBP。
本实施例的器件结构如下：
ITO(20nm)/空穴注入层(HATCN，10nm)/空穴传输层(TCTA，80nm)/光学补偿层(mCBP，70nm)/(供体主体材料(1-2，10nm)：受体主体材料(2-3)：10％磷光材料Ir(mppy)3/电子传输层(TPBi，30nm)/电子注入层(Bphen，10nm)/Mg:Ag(1:4，1nm)/Ag(15nm)
对比例1
该器件结构如下：
ITO(20nm)空穴注入层(HATCN，10nm)/光学补偿层(mCBP，150nm)/mCBP(20nm)：10％磷光材料Ir(mppy)3/电子传输层(TPBi，30nm)/电子注入层(Bphen，10nm)/Mg:Ag(1:4，1nm)/Ag(15nm)
将上面实施例1和对比例1的有机电致发光器件的性能表示在下表1中：
表1.
Figure PCTCN2018073380-appb-000020
由表1的数据可看出，主体材料由供体主体和受体材料预混后，其电流效率和T97寿命均比未 预混(对比例1)高，其中，当供体主体材料(1-2)与受体主体材料(2-3)的质量比为2:3时器件性能最好，与对比例1对比电流效率提升了22％，T97寿命提升了1倍以上，实施例1中的器件寿命T97可以达到1000小时以上。
实施例2
参考实施例1制备有机电致发光器件，其中，供体主体材料为本发明上述供体主体材料1-24，受体主体材料为本发明上述受体主体材料2-10，且二者的质量比为2:3。该器件的性能如表2所示。
实施例3
参考实施例1制备有机电致发光器件，其中，供体主体材料为本发明上述供体主体材料1-30，受体主体材料为本发明上述受体主体材料2-16，且二者的质量比为2:3，该器件的性能如表2所示。
表2.
Figure PCTCN2018073380-appb-000021
本发明实施例还提供一种有机电致发光器件的制备方法，该制备方法包括：在基板上设置阳极；在阳极上设置发光层，该发光层的主体材料由供体主体材料和受体主体材料预混形成，且供体主体材料和受体主体材料置于同一蒸发源中共蒸镀而形成激基复合物，主体材料中掺杂客体材料；以及在发光层上设置阴极。
本发明实施例有效地解决了高亮度下roll-off下降严重的问题，使得器件的稳定性进一步提高，同时减少了客体材料的掺杂浓度，从而降低了产品成本。
在本发明实施例中，该制备方法还包括：在所述阳极与所述发光层之间依次层叠设置空穴注入层和空穴传输层；以及在所述空穴传输层与所述发光层之间设置光学补偿层。具体地，在阳极上设置空穴注入层，在空穴注入层上设置空穴传输层，进一步地，在空穴传输层上设置光学补偿层，该光学补偿层位于发光层之下。
在本发明实施例中，可以通过传统的蒸镀或涂布工艺在基板上依次层叠设置阳极、空穴注入层、空穴传输层、光学补偿层、发光层和阴极等。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换等，均应包含在本发明的保护范围之内。
工业实用性
本发明的有机电致发光器件及其制备方法，通过将发光层的主体材料由供体主体材料和受体主体材料置于同一蒸发源中共蒸镀而形成激基复合物，不仅利于电子与空穴载流子间的平衡，提升了器件的寿命和效率，而且单源蒸镀降低了工艺操作难度，提高了量产的良率。

Claims (14)

  1. 一种有机电致发光器件，其特征在于，包括阳极、阴极以及设置于所述阳极和阴极之间的发光层，所述发光层的主体材料由供体主体材料和受体主体材料预混形成，且所述供体主体材料和受体主体材料置于同一蒸发源中共蒸镀而形成激基复合物，所述主体材料中掺杂客体材料。
  2. 根据权利要求1所述的有机电致发光器件，其特征在于，所述阳极上依次层叠设置有空穴注入层和空穴传输层，所述空穴传输层和发光层间设置有光学补偿层。
  3. 根据权利要求2所述的有机电致发光器件，其特征在于，所述光学补偿层的材料为具有高迁移率的电子阻挡材料，且所述电子阻挡材料的三线态能级大于所述预混的供体主体材料和受体主体材料产生的激基复合物的三线态能级。
  4. 根据权利要求1所述的有机电致发光器件，其特征在于，
    所述供体主体的三线态能级高于所述激基复合物的单线态能级，二者的能隙≥0.2eV；且供体主体的HOMO能级绝对值≤5.3eV；
    所述受体主体的三线态能级高于所述激基复合物的单线态能级，二者的能隙>0.2eV；且受体主体的LUMO能级绝对值>2.0eV。
  5. 根据权利要求4所述的有机电致发光器件，其特征在于，所述供体主体和受体主体蒸发温度均为150℃～500℃。
  6. 根据权利要求4所述的有机电致发光器件，其特征在于，所述供体主体和受体主体蒸镀温度的差值绝对值小于30℃。
  7. 根据权利要求4所述的有机电致发光器件，其特征在于，所述供体主体和受体主体的玻璃转化温度均大于100℃。
  8. 根据权利要求4所述的有机电致发光器件，其特征在于，所述供体主体和受体主体的掺杂质量比为1:9～9:1。
  9. 根据权利要求1至8任一所述的有机电致发光器件，其特征在于，所述供体主体材料的分子通式为：
    Figure PCTCN2018073380-appb-100001
    式中，Ar 1、Ar 2、Ar 3和Ar 4取代基相同或不同，分别独立选自亚芳基或亚杂芳基；
    R 1、R 2、R 3和R 4的结构为
    Figure PCTCN2018073380-appb-100002
    其中，Ar 5、A、Ar 6、B和Ar 7是以稠环方式连接的，共用2个原子，Ar 5、Ar 6和Ar 7相同或不同，分别独立选自苯环、取代的苯环、萘环、取代的萘环、蒽环或取代的蒽环，A为含N原子的五元杂环或六元杂环，B为五元环、五元杂环、六元环或六元杂环；和/或，
    所述受体主体材料的分子通式为：
    Figure PCTCN2018073380-appb-100003
    式中，X 1和X 2相同或不同，分别为-CH-或-N-；
    Y为-O-、-S-、-Se-、-C(CH 3) 2-、-C(C 6H 5) 2-或-C(9-芴基)-；
    Ar 8和Ar 9取代基相同或不同，分别独立选自亚芳基或亚杂芳基；
    R 5和R 6的结构为
    Figure PCTCN2018073380-appb-100004
    其中，Ar 10、C环、Ar 11、D环和Ar 12是以稠环方式连接的，共用2个原子，Ar 10、Ar 11和Ar 12相同或不同，分别独立选自苯环、取代的苯环、萘环或取代的萘环，C环为含N原子的五元杂环或六元杂环，D环为五元环、五元杂环、六元环或六元杂环。
  10. 根据权利要求9所述的有机电致发光器件，其特征在于，所述R 1、R 2、R 3、R 4、R 5和R 6分别独立选自以下任意分子结构中的一种：
    Figure PCTCN2018073380-appb-100005
    Figure PCTCN2018073380-appb-100006
  11. 根据权利要求9所述的有机电致发光器件，其特征在于，所述供体主体材料为具有如下结构的化合物：
    Figure PCTCN2018073380-appb-100007
    Figure PCTCN2018073380-appb-100008
    Figure PCTCN2018073380-appb-100009
    Figure PCTCN2018073380-appb-100010
  12. 根据权利要求9所述的有机电致发光器件，其特征在于，所述受体主体材料为具有如下结构的化合物：
    Figure PCTCN2018073380-appb-100011
    Figure PCTCN2018073380-appb-100012
    Figure PCTCN2018073380-appb-100013
  13. 一种有机电致发光器件的制备方法，其特征在于，包括：
    在基板上设置阳极；
    在所述阳极上设置发光层，所述发光层的主体材料由供体主体材料和受体主体材料预混形成，且所述供体主体材料和受体主体材料置于同一蒸发源中共蒸镀而形成激基复合物，所述主体材料中掺杂客体材料；以及
    在所述发光层上设置阴极。
  14. 根据权利要求13所述的有机电致发光器件的制备方法，其特征在于，还包括：
    在所述阳极与所述发光层之间依次层叠设置空穴注入层和空穴传输层；以及
    在所述空穴传输层与所述发光层之间设置光学补偿层。
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CN108336237A (zh) 2018-07-27
US20190165286A1 (en) 2019-05-30
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JP2020513691A (ja) 2020-05-14
KR20190069584A (ko) 2019-06-19
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US11158821B2 (en) 2021-10-26
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