WO2018053937A1 - 三苯基磷氧衍生物及电致磷光发光器件 - Google Patents

三苯基磷氧衍生物及电致磷光发光器件 Download PDF

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WO2018053937A1
WO2018053937A1 PCT/CN2016/108187 CN2016108187W WO2018053937A1 WO 2018053937 A1 WO2018053937 A1 WO 2018053937A1 CN 2016108187 W CN2016108187 W CN 2016108187W WO 2018053937 A1 WO2018053937 A1 WO 2018053937A1
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light
triphenylphosphorus
oxide derivative
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潘彪
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Wuhan China Star Optoelectronics Technology Co Ltd
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Wuhan China Star Optoelectronics Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6503—Five-membered rings
    • C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
    • C07F9/65068—Five-membered rings having the nitrogen atoms in positions 1 and 3 condensed with carbocyclic rings or carbocyclic ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms

Definitions

  • the invention relates to the field of luminescent materials, in particular to a triphenylphosphorus oxide derivative and an electrophosphorescent light-emitting device.
  • the electron transport rate is many times slower than the hole transport rate; therefore, due to the lower electron mobility, the efficiency of the light-emitting device is lower and the efficiency of the light-emitting device is greatly reduced.
  • Embodiments of the present invention provide a triphenylphosphorus oxide derivative and an electrophosphorescent light-emitting device which can improve the luminous efficiency of the corresponding light-emitting device and have a small roll-off efficiency; to solve the electron mobility of the existing light-emitting device.
  • the present invention provides a triphenylphosphorus oxide derivative for a phosphorescent host and an electron transporting material, wherein the structural formula of the triphenylphosphorus oxide derivative is as follows:
  • R in the structural formula is H or a substituent having electron transporting properties
  • the substituent group having electron transporting properties includes:
  • the R is a structurally identical substituent group
  • the present invention provides a triphenylphosphorus oxide derivative for a phosphorescent host and an electron transporting material, wherein the structural formula of the triphenylphosphorus oxide derivative is as follows:
  • R in the structural formula is H or a substituent having electron transporting properties.
  • the substituent group having electron transporting property includes:
  • An embodiment of the present invention further provides an electrophosphorescent light emitting device, comprising: a substrate, a transparent anode, a hole injection layer, a hole transport layer, an exciton blocking layer, a light emitting layer, an electron transport layer, and an electron injecting layer; a cathode, wherein the light-emitting layer at least partially comprises a triphenylphosphorus oxide derivative; wherein the structural formula of the triphenylphosphorus oxide derivative is as follows:
  • R in the structural formula is H or a substituent having electron transporting properties.
  • the electronic transmission has sexual substituent groups include:
  • the R is a structurally identical substituent group
  • the triphenylphosphorus oxide derivative and the electrophosphorescent light-emitting device of the invention pass the R group of the triphenylphosphorus oxide derivative
  • the use of H or a substituent group having electron transporting property improves the electron mobility and the luminous efficiency of the light emitting device, and reduces the efficiency roll-off of the light emitting device; and solves the low electron mobility of the existing light emitting device, resulting in light emission.
  • the technical problem is that the efficiency of the device is low and the efficiency of the light-emitting device is greatly reduced.
  • FIG. 1 is a schematic structural view of a preferred embodiment of an electrophosphorescent light-emitting device of the present invention
  • FIGS. 2a to 2d are schematic diagrams showing structural levels of a preferred embodiment of the electrophosphorescent light-emitting device of the present invention.
  • FIG. 3 is a graph showing a luminance-voltage-current density of a preferred embodiment of the electrophosphorescent light-emitting device of the present invention.
  • FIG. 4 is a graph showing a power efficiency-current efficiency-luminance curve of a preferred embodiment of the electrophosphorescent light-emitting device of the present invention.
  • Figure 5 is a graph showing the electroluminescence intensity-wavelength of a preferred embodiment of the electrophosphorescent light-emitting device of the present invention.
  • Figure 6 is a graph showing electric field intensity-electron mobility of a preferred embodiment of the electrophosphorescent light-emitting device of the present invention.
  • FIG. 1 is a schematic structural view of a preferred embodiment of an electrophosphorescent light-emitting device of the present invention
  • FIGS. 2a to 2d are electrophosphorescent light-emitting devices of the present invention
  • the electrophosphorescent light-emitting device 10 of the preferred embodiment includes a substrate 11 disposed in order, a transparent anode 12, a hole injection layer 13, a hole transport layer 14, an exciton blocking layer 15, a light-emitting layer 16, an electron transport layer 17, and an electron.
  • the layer 18 and the cathode 19 are injected.
  • the luminescent layer 16 at least partially comprises a triphenylphosphorus oxide derivative.
  • R in the structural formula is H or a substituent group having an electron transporting property.
  • Substituent groups having electron transport properties include, but are not limited to:
  • R is a structurally identical substituent group or all of R, at least two different structural substituent groups are present. All R of the same benzene ring are structurally identical substituent groups, or at least two different structural substituent groups are present in all R of the same benzene ring.
  • the material of the transparent anode 12 of the electrophosphorescent light-emitting device 10 of the preferred embodiment is ITO (Indium Tin Oxides); the material of the hole injection layer 13 is MoO3 (molybdenum trioxide); and the hole transport layer 14 Material is TAPC; exciton blocking layer
  • the material of 15 is TCTA; the guest material of the light-emitting layer 16 is a phosphorescent material Ir(ppy) 3, the host material of the light-emitting layer 16 is a triphenylphosphorus oxide derivative; the material of the electron transport layer 17 is TmPyPB; and the electron injecting layer 18
  • the material is LiF (lithium fluoride); the material of the cathode 19 is Al.
  • the triphenylphosphorus oxide derivative may be pNBIPO, pPBIPO, mNBIPO or mPBIPO.
  • TmPyPB The structural formula of TmPyPB is as follows:
  • TAPC The structural formula of TAPC is as follows:
  • TCTA The structural formula of TCTA is as follows:
  • the hole injection layer 13 has a thickness of 8 nm to 12 nm, preferably 10 nm; the hole transport layer 14 has a thickness of 35 nm to 45 nm, preferably 40 nm; and the exciton blocking layer 15
  • the thickness is 4 nm to 6 nm, preferably 5 nm; the thickness of the light-emitting layer 16 is 15 nm to 25 nm, preferably 20 nm; the thickness of the electron transport layer 17 is 35 nm to 45 nm, preferably 40 nm; and the thickness of the electron injecting layer 18 is 0.8 nm to 1.2.
  • Nm is preferably 1 nm.
  • the thickness of the cathode 19 is from 140 nm to 160 nm, preferably 150 nm.
  • the triphenylphosphorus oxide derivative is 4-(1-methylbenzimidazolyl)-triphenylphosphorus, i.e., pNBIPO.
  • the triphenylphosphorus oxide derivative is 4-(2-methylbenzimidazolyl)-triphenylphosphorus, i.e., pPBIPO.
  • the triphenylphosphorus oxide derivative is 3-(1-methylbenzimidazolyl)-triphenylphosphorus, i.e., mNBIPO.
  • the triphenylphosphorus oxide derivative is 3-(2-methylbenzimidazolyl)-triphenylphosphorus, i.e., mPBIPO.
  • the process for fabricating the electrophosphorescent light-emitting device 10 using pNBIPO as the light-emitting layer material comprises: firstly ultrasonically cleaning the ITO in a cleaning agent and deionized water for 30 minutes, then vacuum drying at 105 degrees for 2 hours, and then placing the ITO in the ion reactor. The CF x plasma treatment was carried out for 1 minute, and transferred to a vacuum chamber to prepare an organic film and a metal electrode. pNBIPO was used as a host material of the light-emitting layer by vacuum plating.
  • the structure of the electrophosphorescent light-emitting device is:
  • ITO/MoO 3 (10 nm) / TAPC (70 nm) / TCTA (5 nm) / pNBIPO-Ir (ppy) 3 (20 nm) / TmPyPB (40 nm) / LiF (1 nm) / Al.
  • N-phenyl-4-p-bromophenylbenzimidazole (1.0 mmol) was dissolved in THF (tetrahydrofuran) (50 ml), cooled to -78 ° C, and n-butyl lithium (1.1 mmol) was added and reacted for 1 hour. Further, diphenylphosphonium chloride (1.2 mmol) was added, and the mixture was warmed to room temperature for 12 hours, and quenched by adding methanol, while adding 30% H 2 O 2 aqueous solution (5 ml) to obtain 4-(2-methylbenzimidazole). Base)-triphenylphosphorus oxygen (pPBIPO); yield: 70%.
  • the process for fabricating the electrophosphorescent light-emitting device 10 using pPBIPO as the light-emitting layer material comprises: firstly ultrasonically cleaning the ITO in a cleaning agent and deionized water for 30 minutes, then vacuum drying at 105 degrees for 2 hours, and then placing the ITO in the ion reactor. The CF x plasma treatment was carried out for 1 minute, and transferred to a vacuum chamber to prepare an organic film and a metal electrode. pPBIPO was used as a host material of the light-emitting layer by a vacuum plating method.
  • the structure of the electrophosphorescent light-emitting device is:
  • ITO/MoO 3 (10 nm) / TAPC (70 nm) / TCTA (5 nm) / pPBIPO - Ir (ppy) 3 (20 nm) / TmPyPB (40 nm) / LiF (1 nm) / Al.
  • the process for fabricating the electrophosphorescent light-emitting device 10 using the mNBIPO as the light-emitting layer material comprises: firstly cleaning the ITO in a cleaning agent and deionized water for 30 minutes, then vacuum drying at 105 degrees for 2 hours, and then placing the ITO into the ion reactor. The CF x plasma treatment was carried out for 1 minute, and transferred to a vacuum chamber to prepare an organic film and a metal electrode. mNBIPO was used as a host material of the light-emitting layer by a vacuum plating method.
  • the structure of the electrophosphorescent light-emitting device is:
  • ITO/MoO 3 (10 nm) / TAPC (70 nm) / TCTA (5 nm) / mPBIPO - Ir (ppy) 3 (20 nm) / TmPyPB (40 nm) / LiF (1 nm) / Al.
  • N-phenyl-3-m-bromophenylbenzimidazole (1.0 mmol) was dissolved in THF (tetrahydrofuran) (50 ml), cooled to -78 ° C, and n-butyl lithium (1.1 mmol) was added and reacted for 1 hour. Further, diphenylphosphonium chloride (1.2 mmol) was added, and the mixture was heated to room temperature for 12 hours, and quenched by adding methanol, while adding 30% H 2 O 2 aqueous solution (5 ml) to obtain 3-(2-methylbenzimidazole). Base)-triphenylphosphoryloxy (mPBIPO); Yield: 70%.
  • the process of fabricating the electrophosphorescent light-emitting device 10 using the mPBIPO as the light-emitting layer material includes: first, ultrasonically cleaning the ITO in a cleaning agent and deionized water for 30 minutes, then vacuum drying at 105 degrees for 2 hours, and then placing the ITO in the ion reactor. The CF x plasma treatment was carried out for 1 minute, and transferred to a vacuum chamber to prepare an organic film and a metal electrode. mPBIPO was used as a host material of the light-emitting layer by a vacuum plating method.
  • the structure of the electrophosphorescent light-emitting device is:
  • ITO/MoO 3 (10 nm) / TAPC (70 nm) / TCTA (5 nm) / mPBIPO - Ir (ppy) 3 (20 nm) / TmPyPB (40 nm) / LiF (1 nm) / Al.
  • FIG. 3 is a graph showing a luminance-voltage-current density of a preferred embodiment of the electrophosphorescent light-emitting device of the present invention
  • FIG. 4 is a power diagram of a preferred embodiment of the electrophosphorescent light-emitting device of the present invention.
  • Efficiency-current efficiency-brightness graph
  • FIG. 5 is an electroluminescence intensity-wavelength diagram of a preferred embodiment of the electrophosphorescent light-emitting device of the present invention
  • FIG. 6 is a preferred embodiment of the electrophosphorescent light-emitting device of the present invention. Electric field strength - electron mobility curve.
  • mNBIPO, mPBIPO, pNBIPO and pPBIPO exhibit good efficiency in the vapor deposition device as electron transport materials, and ⁇ CE,max reached 54.5, 73.4, 68.2 and 65.1 cd/A, ⁇ PE, respectively.
  • Max reached 32.6, 72.2, 58.4, and 64.8 lm/W, respectively, and EQE max reached 14.9%, 20.8%, 19.3%, and 17.9%, respectively.
  • the corresponding device efficiencies of the comparative electrophosphorescent light-emitting devices using the commonly used benzimidazole-based electron transport material TPBi as electron transport materials were 55.6 cd/A, 53.1 lm/W and 15.0%, respectively.
  • the luminous efficiency of the electrophosphorescent light-emitting device corresponding to mNBIPO is slightly lower than that of the electrophosphorescent light-emitting device corresponding to TPBi, because the electron mobility of mNBIPO is lower than that of TPBi.
  • the luminous efficiency of other electrophosphorescent light-emitting devices is better than that of TPBi-corresponding electrophosphorescent light-emitting devices, which indicates that diphenylphosphorus-substituted benzimidazoles are more suitable for small molecule evaporation than TPBi.
  • the triphenylphosphorus oxide derivative provided by the invention has high electron mobility and can realize electron and hole transport rate matching.
  • the triphenylphosphorus oxide derivative The electrophosphorescent light-emitting device as the light-emitting layer has excellent performance, and current efficiency, power efficiency, and external quantum efficiency can reach the highest level of the performance of the current green phosphorescent device.
  • the electrophosphorescent light-emitting device with the triphenylphosphorus oxide derivative as the light-emitting layer has good stability in a large voltage range, effectively reducing the interface energy barrier between the electron transport layer and the light-emitting layer, and avoiding The interface charge accumulation and exciton quenching are beneficial to the improvement of device lifetime, and have broad application prospects in the field of full color display.
  • the triphenylphosphorus oxide derivative and the electrophosphorescent light-emitting device of the present invention improve the electron mobility of the light-emitting device by using H or a substituent group having electron transporting property for the R group of the triphenylphosphorus oxide derivative. And the luminous efficiency, and the efficiency roll-off of the light-emitting device is reduced; the technical problem that the current electron-emitting device has low electron mobility, the efficiency of the light-emitting device is low, and the efficiency of the light-emitting device is greatly reduced is solved.

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Abstract

本发明提供一种三苯基磷氧衍生物，用于磷光主体及电子传输材料，其中三苯基磷氧衍生物的结构通式中的R为H或具有电子传输特性的取代基团。本发明还提供一种电致磷光发光器件，本发明通过将三苯基磷氧衍生物的R基团均使用H或具有电子传输特性的取代基团，提高了发光器件的电子迁移率以及发光效率，并降低了发光器件的效率滚降。

Description

三苯基磷氧衍生物及电致磷光发光器件 技术领域
本发明涉及发光材料领域，特别是涉及一种三苯基磷氧衍生物及电致磷光发光器件。
背景技术
1987年，邓青云教授和Vanslyke采用了超薄膜技术，用透明导电膜作阳极，AlQ3作发光层，三芳胺作空穴传输层，Mg/Ag合金作阴极，制成了双层有机电致发光器件。
1990年，Burroughes等人发现了以共轭高分子PPV为发光层的OLED，从此在全世界范围内掀起了OLED研究的热潮。
由于自旋限制的影响，在日常生活中我们看到的多为荧光现象。最初的OLED技术研究主要集中在荧光器件方向。但是，根据自旋量子统计理论，荧光电致发光器件，其最大内量子效率只有25％，而磷光电致发光器件，则可以达到100％。因此在1999年Forrest和Thompson等将绿光磷光材料Ir(ppy)3以6wt％的浓度掺杂在4，4’-N，N’-二咔唑-联苯(CBP)的主体材料中，获得绿光OLED最大外量子效率(EQE)达到8％，突破了电致荧光器件的理论极限之后，人们对磷光发光材料产生了高度关注。从那之后，电致磷光材料和磷光器件一直是OLED研究的热点。
对于有机半导体材料，其电子传输速率比空穴传输速率要慢很多倍；因此由于电子迁移率较低，导致发光器件的效率较低且发光器件的效率滚降较大。
故，有必要提供一种三苯基磷氧衍生物及电致磷光发光器件，以解决现有技术所存在的问题。
发明内容
本发明实施例提供一种可使相应的发光器件的发光效率较高且效率滚降较小的三苯基磷氧衍生物及电致磷光发光器件；以解决现有的发光器件的电子迁移率较低，导致发光器件的效率较低且发光器件的效率滚降较大的技术问题。
本发明实施例提供一种三苯基磷氧衍生物，用于磷光主体及电子传输材料，其中所述三苯基磷氧衍生物的结构通式如下所示：
Figure PCTCN2016108187-appb-000001
其中，所述结构通式中的R为H或具有电子传输特性的取代基团；
所述具有电子传输特性的取代基团包括：
Figure PCTCN2016108187-appb-000002
所述R为结构相同的取代基团；或
所有的所述R中，至少存在两种不同结构的取代基团。
本发明实施例提供一种三苯基磷氧衍生物，用于磷光主体及电子传输材料，其中所述三苯基磷氧衍生物的结构通式如下所示：
Figure PCTCN2016108187-appb-000003
其中，所述结构通式中的R为H或具有电子传输特性的取代基团。
在本发明所述的三苯基磷氧衍生物中，所述具有电子传输特性的取代基团包括：
Figure PCTCN2016108187-appb-000004
本发明实施例还提供一种电致磷光发光器件，其包括依次设置的基板、透明阳极、空穴注入层、空穴传输层、激子阻隔层、发光层、电子传输层、电子注入层以及阴极，其中所述发光层至少部分包括三苯基磷氧衍生物；其中所述三苯基磷氧衍生物的结构通式如下所示：
Figure PCTCN2016108187-appb-000005
其中，所述结构通式中的R为H或具有电子传输特性的取代基团。
在本发明所述的电致磷光发光器件中，所述具有电子传输特 性的取代基团包括：
Figure PCTCN2016108187-appb-000006
在本发明所述的电致磷光发光器件中，所述R为结构相同的取代基团；或
所有的所述R中，至少存在两种不同结构的取代基团。
相较于现有的三苯基磷氧衍生物及电致磷光发光器件，本发明的三苯基磷氧衍生物及电致磷光发光器件通过将三苯基磷氧衍生物的R基团均使用H或具有电子传输特性的取代基团，提高了发光器件的电子迁移率以及发光效率，并降低了发光器件的效率滚降；解决了现有的发光器件的电子迁移率较低，导致发光器件的效率较低且发光器件的效率滚降较大的技术问题。
为让本发明的上述内容能更明显易懂，下文特举优选实施例，并配合所附图式，作详细说明如下：
附图说明
图1为本发明的电致磷光发光器件的优选实施例的结构示意图；
图2a至图2d为本发明的电致磷光发光器件的优选实施例的结构能级示意图；
图3为本发明的电致磷光发光器件的优选实施例的亮度-电压-电流密度曲线图；
图4为本发明的电致磷光发光器件的优选实施例的功率效率-电流效率-亮度曲线图；
图5为本发明的电致磷光发光器件的优选实施例的电致发光强度-波长曲线图；
图6为本发明的电致磷光发光器件的优选实施例的电场强度-电子迁移率曲线图。
具体实施方式
以下各实施例的说明是参考附加的图式，用以例示本发明可用以实施的特定实施例。本发明所提到的方向用语，例如「上」、「下」、「前」、「后」、「左」、「右」、「内」、「外」、「侧面」等，仅是参考附加图式的方向。因此，使用的方向用语是用以说明及理解本发明，而非用以限制本发明。
在图中，结构相似的单元是以相同标号表示。
请参照图1、图2a、图2b、图2c以及图2d，图1为本发明的电致磷光发光器件的优选实施例的结构示意图；图2a至图2d为本发明的电致磷光发光器件的优选实施例的结构能级示意图。本优选实施例的电致磷光发光器件10包括依次设置的基板11、透明阳极12、空穴注入层13、空穴传输层14、激子阻隔层15、发光层16、电子传输层17、电子注入层18以及阴极19。其中发光层16至少部分包括三苯基磷氧衍生物。
该三苯基磷氧衍生物的结构通式如下所示：
Figure PCTCN2016108187-appb-000007
其中结构通式中的R为H或具有电子传输特性的取代基团。
具有电子传输特性的取代基团包括但不限于：
Figure PCTCN2016108187-appb-000008
其中R为结构相同的取代基团或所有的R中，至少存在两种不同结构的取代基团。同一苯环的所有R为结构相同的取代基团，或同一苯环的所有R中至少存在两种不同结构的取代基团。
本优选实施例的电致磷光发光器件10的透明阳极12的材料为ITO(Indium Tin Oxides，氧化铟锡)；空穴注入层13的材料为MoO3(三氧化钼)；空穴传输层14的材料为TAPC；激子阻挡层 15的材料为TCTA；发光层16的客体材料为磷光材料Ir(ppy)3，发光层16的主体材料为三苯基磷氧衍生物；电子传输层17的材料为TmPyPB；电子注入层18的材料为LiF(氟化锂)；阴极19的材料为Al。
其中三苯基磷氧衍生物可为pNBIPO、pPBIPO、mNBIPO或mPBIPO。
其中pNBIPO的结构通式如下所示：
Figure PCTCN2016108187-appb-000009
pPBIPO的结构通式如下所示：
Figure PCTCN2016108187-appb-000010
mNBIPO的结构通式如下所示：
Figure PCTCN2016108187-appb-000011
mPBIPO的结构通式如下所示：
Figure PCTCN2016108187-appb-000012
Ir(ppy)3的结构通式如下所示：
Figure PCTCN2016108187-appb-000013
TmPyPB的结构通式如下所示：
Figure PCTCN2016108187-appb-000014
TAPC的结构通式如下所示：
Figure PCTCN2016108187-appb-000015
TCTA的结构通式如下所示：
Figure PCTCN2016108187-appb-000016
本优选实施例的电致磷光发光器件中，空穴注入层13的厚度为8nm至12nm，优选为10nm；空穴传输层14的厚度为35nm至45nm，优选为40nm；激子阻挡层15的厚度为4nm至6nm，优选为5nm；发光层16的厚度为15nm-25nm，优选为20nm；电子传输层17的厚度为35nm-45nm，优选为40nm；电子注入层18的厚度为0.8nm至1.2nm，优选为1nm。阴极19的厚度为140nm至160nm，优选为150nm。
四种不同发光层的电致磷光发光器件的结构能级请参照图2a至图2d。
当三苯基磷氧衍生物的一个R为
Figure PCTCN2016108187-appb-000017
其余R均为H时，该三苯基磷氧衍生物为4-(1-甲基苯并咪唑基)-三苯基磷氧，即pNBIPO。
当三苯基磷氧衍生物的一个R为
Figure PCTCN2016108187-appb-000018
其余R均为H时，该三苯基磷氧衍生物为4-(2-甲基苯并咪唑基)-三苯基磷氧，即pPBIPO。
当三苯基磷氧衍生物的一个R为
Figure PCTCN2016108187-appb-000019
其余R均为H时，该三苯基磷氧衍生物为3-(1-甲基苯并咪唑基)-三苯基磷氧， 即mNBIPO。
当三苯基磷氧衍生物的一个R为
Figure PCTCN2016108187-appb-000020
其余R均为H时，该三苯基磷氧衍生物为3-(2-甲基苯并咪唑基)-三苯基磷氧，即mPBIPO。
其中本优选实施例的pNBIPO可通过下列方法合成：
将2-苯基-4-N-对溴苯基苯并咪唑(1.0mmol)溶解于THF(四氢呋喃)(50ml)中，冷却至-78℃，加入正丁基锂(1.1mmol)，反应1小时，再加入二苯基氯化磷(1.2mmol)，升温至室温反应12小时，加入甲醇猝灭反应，同时加入30％H2O2水溶液(5ml)氧化得到4-(1-甲基苯并咪唑基)-三苯基磷氧(pNBIPO)；产率：70％。
使用pNBIPO作为发光层材料制作电致磷光发光器件10的流程包括：先将ITO在清洗剂和去离子水中以超声波清洗30分钟，然后在105度真空干燥2小时，再将ITO放入离子反应器中进行1分钟的CFx等离子处理，传送到真空室内制备有机膜和金属电极。通过真空电镀的方法将pNBIPO作为发光层的主体材料。该电致磷光发光器件的结构为：
ITO/MoO3(10nm)/TAPC(70nm)/TCTA(5nm)/pNBIPO-Ir(ppy)3(20nm)/TmPyPB(40nm)/LiF(1nm)/Al。
其中本优选实施例的pPBIPO可通过下列方法合成：
将N-苯基-4-对溴苯基苯并咪唑(1.0mmol)溶解于THF(四氢呋喃)(50ml)中，冷却至-78℃，加入正丁基锂(1.1mmol)，反应1小时，再加入二苯基氯化磷(1.2mmol)，升温至室温反应12小时，加入甲醇猝灭反应，同时加入30％H2O2水溶液(5ml)氧化得到4-(2-甲基苯并咪唑基)-三苯基磷氧(pPBIPO)；产率：70％。
使用pPBIPO作为发光层材料制作电致磷光发光器件10的流 程包括：先将ITO在清洗剂和去离子水中以超声波清洗30分钟，然后在105度真空干燥2小时，再将ITO放入离子反应器中进行1分钟的CFx等离子处理，传送到真空室内制备有机膜和金属电极。通过真空电镀的方法将pPBIPO作为发光层的主体材料。该电致磷光发光器件的结构为：
ITO/MoO3(10nm)/TAPC(70nm)/TCTA(5nm)/pPBIPO-Ir(ppy)3(20nm)/TmPyPB(40nm)/LiF(1nm)/Al。
其中本优选实施例的mNBIPO可通过下列方法合成：
将2-苯基-3-间溴苯基苯并咪唑(1.0mmol)溶解于THF(四氢呋喃)(50ml)中，冷却至-78℃，加入正丁基锂(1.1mmol)，反应1小时，再加入二苯基氯化磷(1.2mmol)，升温至室温反应12小时，加入甲醇猝灭反应，同时加入30％H2O2水溶液(5ml)氧化得到3-(1-甲基苯并咪唑基)-三苯基磷氧(mNBIPO)；产率：70％。
使用mNBIPO作为发光层材料制作电致磷光发光器件10的流程包括：先将ITO在清洗剂和去离子水中以超声波清洗30分钟，然后在105度真空干燥2小时，再将ITO放入离子反应器中进行1分钟的CFx等离子处理，传送到真空室内制备有机膜和金属电极。通过真空电镀的方法将mNBIPO作为发光层的主体材料。该电致磷光发光器件的结构为：
ITO/MoO3(10nm)/TAPC(70nm)/TCTA(5nm)/mPBIPO-Ir(ppy)3(20nm)/TmPyPB(40nm)/LiF(1nm)/Al。
其中本优选实施例的mPBIPO可通过下列方法合成：
将N-苯基-3-间溴苯基苯并咪唑(1.0mmol)溶解于THF(四氢呋喃)(50ml)中，冷却至-78℃，加入正丁基锂(1.1mmol)，反应1小时，再加入二苯基氯化磷(1.2mmol)，升温至室温反应12小时，加入甲醇猝灭反应，同时加入30％H2O2水溶液(5ml)氧化得到3-(2-甲基苯并咪唑基)-三苯基磷氧(mPBIPO)；产率：70％。
使用mPBIPO作为发光层材料制作电致磷光发光器件10的流程包括：先将ITO在清洗剂和去离子水中以超声波清洗30分钟，然后在105度真空干燥2小时，再将ITO放入离子反应器中进行1分钟的CFx等离子处理，传送到真空室内制备有机膜和金属电极。通过真空电镀的方法将mPBIPO作为发光层的主体材料。该电致磷光发光器件的结构为：
ITO/MoO3(10nm)/TAPC(70nm)/TCTA(5nm)/mPBIPO-Ir(ppy)3(20nm)/TmPyPB(40nm)/LiF(1nm)/Al。
请参照图3至图6，图3为本发明的电致磷光发光器件的优选实施例的亮度-电压-电流密度曲线图；图4为本发明的电致磷光发光器件的优选实施例的功率效率-电流效率-亮度曲线图；图5为本发明的电致磷光发光器件的优选实施例的电致发光强度-波长曲线图；图6为本发明的电致磷光发光器件的优选实施例的电场强度-电子迁移率曲线图。
从图中可以看出，mNBIPO、mPBIPO、pNBIPO和pPBIPO作为电子传输材料在蒸镀器件中表现出良好的效率，ηCE，max分别达到了54.5、73.4、68.2和65.1cd/A，ηPE，max分别达到了32.6、72.2、58.4和64.8lm/W，EQEmax分别达到14.9％、20.8％、19.3％和17.9％。而以常用的苯并咪唑类电子传输材料TPBi作电子传输材料的对比电致磷光发光器件相应的器件效率分别为55.6cd/A、53.1lm/W和15.0％。从发光效率来看，mNBIPO对应的电致磷光发光器件的发光效率略低于TPBi对应的电致磷光发光器件的发光效率，这是由于mNBIPO的电子迁移率低于TPBi的电子迁移率。其他的电致磷光发光器件的发光效率均优于TPBi对应的电致磷光发光器件的发光效率，这表明二苯基磷氧取代苯并咪唑类化合物比TPBi更适合于用来作为小分子蒸镀绿色磷光器件中的电子传输材料。
本发明所提供的三苯基磷氧衍生物具有较高的电子迁移率，能够实现电子和空穴的传输速率匹配。且以该三苯基磷氧衍生物 作为发光层的电致磷光发光器件的性能优异，电流效率，功率效率和外量子效率均能达到目前绿色磷光器件的性能中的最高水平。同时以该三苯基磷氧衍生物作为发光层的电致磷光发光器件在较大的电压范围内具有很好的稳定性，有效减少了电子传输层和发光层之间的界面能垒，避免了界面电荷积累及激子淬灭，有利于器件寿命的提高，在全彩显示领域有广泛的应用前景。
本发明的三苯基磷氧衍生物及电致磷光发光器件通过将三苯基磷氧衍生物的R基团均使用H或具有电子传输特性的取代基团，提高了发光器件的电子迁移率以及发光效率，并降低了发光器件的效率滚降；解决了现有的发光器件的电子迁移率较低，导致发光器件的效率较低且发光器件的效率滚降较大的技术问题。
综上所述，虽然本发明已以优选实施例揭露如上，但上述优选实施例并非用以限制本发明，本领域的普通技术人员，在不脱离本发明的精神和范围内，均可作各种更动与润饰，因此本发明的保护范围以权利要求界定的范围为准。

Claims (15)

  1. 一种三苯基磷氧衍生物，用于磷光主体及电子传输材料，其中所述三苯基磷氧衍生物的结构通式如下所示：
    Figure PCTCN2016108187-appb-100001
    其中，所述结构通式中的R为H或具有电子传输特性的取代基团；
    所述具有电子传输特性的取代基团包括：
    Figure PCTCN2016108187-appb-100002
    所述R为结构相同的取代基团；或
    所有的所述R中，至少存在两种不同结构的取代基团。
  2. 根据权利要求1所述的三苯基磷氧衍生物，其中同一苯环 的所有R为结构相同的取代基团；或同一苯环的所有R中至少存在两种不同结构的取代基团。
  3. 一种三苯基磷氧衍生物，用于磷光主体及电子传输材料，其中所述三苯基磷氧衍生物的结构通式如下所示：
    Figure PCTCN2016108187-appb-100003
    其中，所述结构通式中的R为H或具有电子传输特性的取代基团。
  4. 根据权利要求3所述的三苯基磷氧衍生物，其中所述具有电子传输特性的取代基团包括：
    Figure PCTCN2016108187-appb-100004
  5. 根据权利要求3所述的三苯基磷氧衍生物，其中所述R为结构相同的取代基团；或
    所有的所述R中，至少存在两种不同结构的取代基团。
  6. 根据权利要求5所述的三苯基磷氧衍生物，其中同一苯环的所有R为结构相同的取代基团；或同一苯环的所有R中至少存在两种不同结构的取代基团。
  7. 一种电致磷光发光器件，其中包括依次设置的基板、透明阳极、空穴注入层、空穴传输层、激子阻隔层、发光层、电子传输层、电子注入层以及阴极，其中所述发光层至少部分包括三苯基磷氧衍生物；其中所述三苯基磷氧衍生物的结构通式如下所示：
    Figure PCTCN2016108187-appb-100005
    其中，所述结构通式中的R为H或具有电子传输特性的取代基团。
  8. 根据权利要求7所述的电致磷光发光器件，其中所述具有电子传输特性的取代基团包括：
    Figure PCTCN2016108187-appb-100006
  9. 根据权利要求7所述的电致磷光发光器件，其中所述R为结构相同的取代基团；或
    所有的所述R中，至少存在两种不同结构的取代基团。
  10. 根据权利要求9所述的电致磷光发光器件，其中同一苯环的所有R为结构相同的取代基团；或同一苯环的所有R中至少存在两种不同结构的取代基团。
  11. 根据权利要求7所述的电致磷光发光器件，其中所述透明阳极为ITO，所述空穴注入层为MoO3，所述空穴传输层为TAPC，所述激子阻隔层为TCTA，所述发光层为掺杂Ir(ppy)3的所述三苯基磷氧衍生物，所述电子传输层为TmPyPB，所述电子注入层为LiF，所述阴极为Al。
  12. 根据权利要求11所述的电致磷光发光器件，其中所述三苯基磷氧衍生物为pNBIPO、pPBIPO、mNBIPO或mPBIPO。
  13. 根据权利要求11所述的电致磷光发光器件，其中所述空穴注入层的厚度为8nm至12nm，所述空穴传输层的厚度为60nm至80nm，所述激子阻隔层的厚度为4nm至6nm，所述发光层的厚度为15nm至25nm，所述电子传输层的厚度为35nm至45nm，所述电子注入层的厚度为0.8nm至1.2nm。
  14. 根据权利要求11所述的电致磷光发光器件，其中
    所述TAPC的结构通式如下所示：
    Figure PCTCN2016108187-appb-100007
    所述TCTA的结构通式如下所示：
    Figure PCTCN2016108187-appb-100008
    所述Ir(ppy)3的结构通式如下所示：
    Figure PCTCN2016108187-appb-100009
    所述TmPyPB的结构通式如下所示：
    Figure PCTCN2016108187-appb-100010
  15. 根据权利要求12所述的电致磷光发光器件，其中
    所述pNBIPO的结构通式如下所示：
    Figure PCTCN2016108187-appb-100011
    所述pPBIPO的结构通式如下所示：
    Figure PCTCN2016108187-appb-100012
    所述mNBIPO的结构通式如下所示：
    Figure PCTCN2016108187-appb-100013
    所述mPBIPO的结构通式如下所示：
    Figure PCTCN2016108187-appb-100014
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